Shampoo containing a gel network

ABSTRACT

Shampoo compositions comprise (a) from about 5% to about 50% of one or more detersive surfactants, by weight of the shampoo composition; (b) a dispersed gel network phase comprising, by weight of the shampoo composition, (i) at least about 0.05% of one or more fatty amphiphiles; (ii) at least about 0.01% of one or more secondary surfactants; and (iii) water; and (c) at least about 20% of an aqueous carrier, by weight of the shampoo composition. A process for preparing a shampoo composition comprises the steps of: (a) combining a fatty amphiphile, a secondary surfactant, and water at a temperature sufficient to allow partitioning of the secondary surfactant and the water into the fatty amphiphile to form a pre-mix; (b) cooling the pre-mix below the chain melt temperature of the fatty amphiphile to form a gel network; (c) adding the gel network to one or more detersive surfactants and an aqueous carrier to form a shampoo composition.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of prior U.S. applicationSer. No. 10/454,433 now granted as U.S. Pat. No. 7,303,744, filed onJun. 4, 2003; which claims the benefit of U.S. Provisional ApplicationSer. No. 60/385,641, filed on Jun. 4, 2002.

FIELD OF THE INVENTION

The present invention relates to a hair cleansing and conditioningshampoo containing a gel network comprising a fatty amphiphile.

BACKGROUND OF THE INVENTION

Human hair becomes soiled due to its contact with the surroundingenvironment and from the sebum secreted by the scalp. The soiling ofhair causes it to have a dirty feel and an unattractive appearance. Thesoiling of the hair necessitates shampooing with frequent regularity.

Shampooing cleans the hair by removing excess soil and sebum. However,shampooing can leave the hair in a wet, tangled, and generallyunmanageable state. Once the hair dries, it is often left in a dry,rough, lusterless, or frizzy condition due to removal of the hair'snatural oils and other natural conditioning and moisturizing components.The hair can further be left with increased levels of static upondrying, which can interfere with combing and result in a conditioncommonly referred to as “fly-away hair.”

A variety of approaches have been developed to alleviate theseafter-shampoo problems. These approaches range from post-shampooapplication of hair conditioners such as leave-on and rinse-offproducts, to hair conditioning shampoos which attempt to both cleanseand condition the hair from a single product.

In order to provide hair conditioning benefits in a cleansing shampoobase, a wide variety of conditioning actives have been proposed.However, many of these actives have the disadvantage of leaving the hairfeeling soiled or coated and of interfering with the cleansing efficacyof the shampoo.

Coacervate formation in a shampoo composition is known to beadvantageous for providing conditioning benefits to the hair. The use ofcationic polymers to form coacervate is known in the art, such as in PCTpublications WO 93/08787 and WO 95/01152. However, these shampoocompositions are good for delivering wet hair conditioning but are notcapable of delivering satisfactory dry hair smooth feel.

Based on the foregoing, there is a need for a conditioning shampoo whichcan provide improved conditioning benefit for dry hair, while notinterfering with the cleansing efficacy, nor providing negative feel tothe hair when it is dried. Specifically, there is a need to provide longlasting moisturized feel, smooth feel, and manageability control to thehair when the hair is dried, yet not leave the hair feeling greasy, aswell as to provide softness and ease of combing when the hair is wet.

None of the existing art provides all of the advantages and benefits ofthe present invention.

SUMMARY OF THE INVENTION

The present invention is directed to a shampoo composition comprising:(a) from about 5% to about 50% of one or more detersive surfactants, byweight of the shampoo composition; (b) a dispersed gel network phasecomprising: (i) at least about 0.05% of one or more fatty amphiphiles,by weight of the shampoo composition; (ii) at least about 0.01% of oneor more secondary surfactants, by weight of the shampoo composition; and(iii) water; and (c) at least about 20% of an aqueous carrier, by weightof the shampoo composition.

The present invention also is directed to a process of making theshampoo composition described above.

The present invention is further directed to a method of using theshampoo composition described above.

These and other features, aspects, and advantages of the presentinvention will become evident to those skilled in the art from a readingof the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified. The term “weight percent” may be denoted as “wt. %” herein.

All molecular weights as used herein are weight average molecularweights expressed as grams/mole, unless otherwise specified.

The term “charge density”, as used herein, refers to the ratio of thenumber of positive charges on a polymer to the molecular weight of saidpolymer.

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. The compositionsand methods/processes of the present invention can comprise, consist of,and consist essentially of the essential elements and limitations of theinvention described herein, as well as any of the additional or optionalingredients, components, steps, or limitations described herein.

The term “polymer” as used herein shall include materials whether madeby polymerization of one type of monomer or made by two (i.e.,copolymers) or more types of monomers.

The term “shampoo” as used herein means a composition for cleansing andconditioning hair or skin, including scalp, face, and body.

The term “suitable for application to human hair” as used herein meansthat the compositions or components thereof so described are suitablefor use in contact with human hair and the scalp and skin without unduetoxicity, incompatibility, instability, allergic response, and the like.

The term “water soluble” as used herein means that the material issoluble in water in the present composition. In general, the materialshould be soluble at 25° C. at a concentration of 0.1% by weight of thewater solvent, preferably at 1%, more preferably at 5%, more preferablyat 15%.

The shampoo compositions of the present invention comprise one or moredetersive surfactants, a dispersed gel network phase, and an aqueouscarrier. Each of these essential components, as well as preferred oroptional components, is described in detail hereinafter.

A. Detersive Surfactant

The shampoo compositions of the present invention comprise one or moredetersive surfactants. The detersive surfactant component is included inshampoo compositions of the present invention to provide cleansingperformance. The detersive surfactant may be selected from anionicdetersive surfactant, zwitterionic or amphoteric detersive surfactant,or a combination thereof. Such surfactants should be physically andchemically compatible with the essential components described herein, orshould not otherwise unduly impair product stability, aesthetics orperformance.

Suitable anionic detersive surfactant components for use in thecomposition herein include those which are known for use in hair care orother personal care cleansing compositions. The concentration of theanionic surfactant component in the composition should be sufficient toprovide the desired cleaning and lather performance, and generally rangefrom about 5% to about 50%, preferably from about 8% to about 30%, morepreferably from about 10% to about 25%, even more preferably from about12% to about 22%, by weight of the composition.

Preferred anionic surfactants suitable for use in the compositions arethe alkyl and alkyl ether sulfates. These materials have the respectiveformulae ROSO₃M and RO(C₂H₄O)_(X)SO₃M, wherein R is alkyl or alkenyl offrom about 8 to about 18 carbon atoms, x is an integer having a value offrom 1 to 10, and M is a cation such as ammonium, alkanolamines, such astriethanolamine, monovalent metals, such as sodium and potassium, andpolyvalent metal cations, such as magnesium, and calcium.

Preferably, R has from about 8 to about 18 carbon atoms, more preferablyfrom about 10 to about 16 carbon atoms, even more preferably from about12 to about 14 carbon atoms, in both the alkyl and alkyl ether sulfates.The alkyl ether sulfates are typically made as condensation products ofethylene oxide and monohydric alcohols having from about 8 to about 24carbon atoms. The alcohols can be synthetic or they can be derived fromfats, e.g., coconut oil, palm kernel oil, tallow. Lauryl alcohol andstraight chain alcohols derived from coconut oil or palm kernel oil arepreferred. Such alcohols are reacted with from about 0 and about 10,preferably from about 2 to about 5, more preferably about 3, molarproportions of ethylene oxide, and the resulting mixture of molecularspecies having, for example, an average of 3 moles of ethylene oxide permole of alcohol, is sulfated and neutralized.

Other suitable anionic detersive surfactants are the water-soluble saltsof organic, sulfuric acid reaction products conforming to the formulaR¹—SO₃-M wherein R¹ is a straight or branched chain, saturated,aliphatic hydrocarbon radical having from about 8 to about 24,preferably from about 10 to about 18, carbon atoms; and M is a cationdescribed hereinbefore.

Still other suitable anionic detersive surfactants are the reactionproducts of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil or palm kernel oil; sodium or potassium salts of fattyacid amides of methyl tauride in which the fatty acids, for example, arederived from coconut oil or palm kernel oil. Other similar anionicsurfactants are described in U.S. Pat. Nos. 2,486,921; 2,486,922; and2,396,278.

Other anionic detersive surfactants suitable for use in the compositionsare the succinnates, examples of which include disodiumN-octadecylsulfosuccinnate; disodium lauryl sulfosuccinate; diammoniumlauryl sulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinnate; diamyl ester ofsodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid;and dioctyl esters of sodium sulfosuccinic acid.

Other suitable anionic detersive surfactants include olefin sulfonateshaving from about 10 to about 24 carbon atoms. In addition to the truealkene sulfonates and a proportion of hydroxy-alkanesulfonates, theolefin sulfonates can contain minor amounts of other materials, such asalkene disulfonates depending upon the reaction conditions, proportionof reactants, the nature of the starting olefins and impurities in theolefin stock and side reactions during the sulfonation process. Anon-limiting example of such an alpha-olefin sulfonate mixture isdescribed in U.S. Pat. No. 3,332,880.

Another class of anionic detersive surfactants suitable for use in thecompositions is the beta-alkyloxy alkane sulfonates. These surfactantsconform to the formula:

where R¹ is a straight chain alkyl group having from about 6 to about 20carbon atoms, R² is a lower alkyl group having from about 1 to about 3carbon atoms, preferably 1 carbon atom, and M is a water-soluble cationas described hereinbefore.

Preferred anionic detersive surfactants for use in the compositionsinclude ammonium lauryl sulfate, ammonium laureth sulfate, triethylaminelauryl sulfate, triethylamine laureth sulfate, triethanolamine laurylsulfate, triethanolamine laureth sulfate, monoethanolamine laurylsulfate, monoethanolamine laureth sulfate, diethanolamine laurylsulfate, diethanolamine laureth sulfate, lauric monoglyceride sodiumsulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium laurylsulfate, potassium laureth sulfate, sodium lauryl sarcosinate, sodiumlauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate, and combinations thereof.

Suitable zwitterionic or amphoteric detersive surfactants for use in thecomposition herein include those which are known for use in hair care orother personal cleansing compositions. Concentration of such amphotericdetersive surfactants preferably ranges from about 0.5% to about 20%,preferably from about 1% to about 10%. Non-limiting examples of suitablezwitterionic or amphoteric surfactants are described in U.S. Pat. Nos.5,104,646 and 5,106,609, both to Bolich Jr. et al.

Amphoteric detersive surfactants suitable for use in the composition arewell known in the art, and include those surfactants broadly describedas derivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight or branched chain and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic group such as carboxy, sulfonate,sulfate, phosphate, or phosphonate. Preferred amphoteric detersivesurfactants for use in the present invention include cocoamphoacetate,cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate, and mixturesthereof.

Zwitterionic detersive surfactants suitable for use in the compositionare well known in the art, and include those surfactants broadlydescribed as derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic group such as carboxy, sulfonate, sulfate, phosphate orphosphonate. Zwitterionics such as betaines are preferred.

The compositions of the present invention may further compriseadditional surfactants for use in combination with the anionic detersivesurfactant component described hereinbefore. Suitable additionalsurfactants include cationic and nonionic surfactants.

Cationic surfactants suitable for use in the present invention includequaternary ammonium salts or amido-amines having at least one fattychain containing at least about 8 carbon atoms and mixture thereof.

Suitable quaternary ammonium salts have the following general formula:N⁺(R₁R₂R₃R₄)X⁻wherein R₁ is selected from linear and branched radicals comprising fromabout 8 to about 30 carbon atoms; R₂ is selected from linear andbranched radicals comprising from about 8 to 30 carbon atoms or the samegroup as radicals R₃ and R₄; R₃ and R₄ are independently selected fromlinear and branched aliphatic radicals comprising from about 1 to about4 carbon atoms, and aromatic radicals such as aryl and alkylaryl,wherein the aliphatic radicals may comprise at least one hetero atomsuch as oxygen, nitrogen, sulphur, and halogens, and the aliphaticradicals are chosen, for example, from alkyl, alkoxy, and alkylamideradicals; and X— is an anion selected from halides such as chloride,bromide, and iodide, (C₂-C₆)alkyl sulphates, such as methyl sulphate,phosphates, alkyl, and alkylaryl sulphonates, and anions derived fromorganic acids, such as acetate and lactate.

Non-limiting examples of such suitable cationic surfactants includecetrimonium chloride, stearimonium chloride, behentrimonium chloride,behenamidopropyltrimonium methosulfate, stearamidopropyltrimoniumchloride, arachidtrimonium chloride, and mixtures thereof.

Suitable amido-amine cationic surfactants have the following generalformula:R′₁—CONH(CH₂)nNR′₂R′₃wherein R′₁ is selected from linear and branched radicals comprisingabout 8 to about 30 carbon atoms; R′₂ and R′₃ are independently selectedfrom hydrogen, linear and branched aliphatic radicals comprising fromabout 1 to about 4 carbon atoms, and aromatic radicals such as aryl andalkylaryl, wherein the aliphatic radicals may comprise at least onehetero atom such as oxygen, nitrogen, sulphur, and halogens, and thealiphatic radicals are chosen, for example, from alkyl, alkoxy andalkylamide radicals; and n is an integer from about 1 to about 4.

Non-limiting examples of such suitable amido-amines includestearamidopropyldimethylamine, behenamidopropyldimethylamine,behenamidopropyldiethylamine, behenamidoethyldiethyl-amine,behenamidoethyldimethylamine, arachidamidopropyldimethylamine,arachidamido-propyldiethylamine, arachidamidoethyldiethylamine,arachidamidoethyldimethylamine, and mixtures thereof.

Suitable nonionic surfactants include nonionic surfactants having an HLBof 7 or more and comprising one or more polyethyleneoxide chains whereineach polyethyleneoxide chain contains on average at least about 5ethylene oxide units.

Nonionic surfactants comprising one or more polyethyleneoxide chainwherein each polyethyleneoxide chain contains on average at least about5 ethylene oxide units include polyoxyethylene alkyl ethers,polyethyleneglycol fatty acid esters, polyoxyethylene castor oil,polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty amidesand their monoethanolamine and diethanolamine derivatives, andpolyethoxylated fatty amines, with a number of ethylene oxide groups ofat least about 50, and mixtures thereof.

Among preferred nonionic surfactants comprising one or morepolyethyleneoxide chain include polyoxyethylene alkyl ethers having atleast about 5, preferably from about 10 to 20, ethylene oxide units.Examples of such nonionic surfactants are steareth-10 and steareth-15.

Also suitable for use as nonionic surfactants are nonionic surfactantshaving an HLB of 7 or more which are free of polyethyleneoxide chains.Nonionic surfactants free of polyethyleneoxide chains includepolyglycerolated fatty acids, polyglycerolated fatty amides,polyglycerolated alkyl phenols, polyglycerolated α-diols,polyglycerolated alcohols, alkyl polyglucosides, and sugar esters.Preferably, suitable nonionic surfactants free of polyethyleneoxidechains are selected from alkyl polyglucosides, sugar esters,polyglyceryl fatty acid esters, alkyl polyglyceryl ethers, and mixturesthereof.

Additionally, among suitable nonionic surfactants are alkylpolysaccharide (APS) surfactants such as the alkyl polyglycosides. Suchsurfactants are described in U.S. Pat. No. 4,565,647 to Llenado, issuedJan. 21, 1986, which discloses APS surfactants having a hydrophobicgroup with about 6 to about 30 carbon atoms and polysaccharide (e.g.,polyglycoside) as the hydrophilic group. Optionally, there can be apolyalkylene-oxide group joining the hydrophobic and hydrophilicmoieties. The alkyl group (i.e., the hydrophobic moiety) can besaturated or unsaturated, branched or unbranched, and unsubstituted orsubstituted (e.g., with hydroxy or cyclic rings).

Also among suitable nonionic surfactants are polyethylene glycol (PEG)glyceryl fatty esters, such as those of the formulaR(O)OCH₂CH(OH)CH₂(OCH₂CH₂)_(n)OH, wherein n is from about 5 to about200, preferably from about 20 to about 100, and R is an aliphatichydrocarbyl having from about 8 to about 20 carbon atoms.

Any such surfactant known in the art for use in hair or personal careproducts may be used, provided that the additional surfactant is alsochemically and physically compatible with the essential components ofthe composition, or does not otherwise unduly impair productperformance, aesthetics or stability. The concentration of theadditional surfactants in the composition may vary with the cleansing orlather performance desired, the optional surfactant selected, thedesired product concentration, the presence of other components in thecomposition, and other factors well known in the art.

Non-limiting examples of other anionic, zwitterionic, amphoteric,cationic, nonionic, or optional additional surfactants suitable for usein the compositions are described in McCutcheon's, Emulsifiers andDetergents, 1989 Annual, published by M. C. Publishing Co., and U.S.Pat. Nos. 3,929,678; 2,658,072; 2,438,091; and 2,528,378.

B. Dispersed Gel Network Phase

The shampoo compositions of the present invention comprise a dispersedgel network phase comprising a fatty amphiphile. The gel network phaseis included in shampoo compositions of the present invention to provideconditioning benefits. As used herein, the term “gel network” refers toa lamellar or vesicular solid crystalline phase which comprises at leastone fatty amphiphile as specified below, at least one secondarysurfactant as specified below, and water or other suitable solvents. Thelamellar or vesicular phase comprises bi-layers made up of a first layercomprising the fatty amphiphile and the secondary surfactant andalternating with a second layer comprising the water or other suitablesolvent. The term “solid crystalline”, as used herein, refers to thestructure of the lamellar or vesicular phase which forms at atemperature below the chain melt temperature of the layer in the gelnetwork comprising the one or more fatty amphiphiles, the chain melttemperature being at least about 27° C. The chain melt temperature maybe measured by differential scanning calorimetry, a method of which isdescribed in the Examples below.

Gel networks which comprise, for example, fatty alcohols have been usedfor years in cosmetic creams and hair conditioners. Such cosmetic creamsand hair conditioners, however, typically contain very low amounts, ifany, of detersive surfactant. Thus, such known products do not provide acombination of cleansing and conditioning to the hair or skin.

Gel networks, generally, are further described by G. M. Eccleston,“Functions of Mixed Emulsifiers and Emulsifying Waxes in DermatologicalLotions and Creams”, Colloids and Surfaces A: Physiochem. and Eng.Aspects 123-124 (1997) 169-182; and by G. M Eccleston, “TheMicrostructure of Semisolid Creams”, Pharmacy International, Vol. 7,63-70 (1986).

In an embodiment of the present invention, the dispersed gel networkphase is pre-formed. The term “pre-formed”, as used herein, means thatthe mixture of the fatty amphiphile, secondary surfactant, and water orother suitable solvent is substantially a solid crystalline phase whenadded to the other components of the shampoo composition.

According to this embodiment of the present invention, the gel networkcomponent of the present invention is prepared as a separate pre-mix,which, after being cooled, is subsequently incorporated with thedetersive surfactant and the other components of the shampoocomposition. More specifically, the gel network component of the presentinvention may be prepared by heating the fatty amphiphile, the secondarysurfactant, and water to a level in the range of about 75° C. to about90° C. and mixing. This mixture is cooled to a level in the range ofabout 27° C. to about 35° C. by, for example, passing the mixturethrough a heat exchanger. As a result of this cooling step, the fattyamphiphile and the secondary surfactant crystallize to form a solidcrystalline gel network.

Alternative methods of preparing the gel network component includesonication and/or milling of the fatty amphiphile, the secondarysurfactant, and water, while these components are heated, to reduce theparticle size of the melted fatty amphiphile phase. This results in anincrease in surface area of the fatty amphiphile phase, which allows thesecondary surfactant and the water to swell the fatty amphiphile phase.Another suitable variation in preparing the gel network includes heatingand mixing the fatty amphiphile and the secondary surfactant first, andthen adding that mixture to the water.

The cooled and pre-formed gel network component subsequently is added tothe other components of the shampoo composition, including the detersivesurfactant component. While not intending to be limited by theory, it isbelieved that incorporation of the cooled and pre-formed gel networkcomponent with the detersive surfactant and other components of theshampoo composition allows the formation of a substantially equilibratedlamellar dispersion (“ELD”) in the final shampoo composition. The ELD isa dispersed lamellar or vesicular phase resulting from the pre-formedgel network component substantially equilibrating with the detersivesurfactants, water, and other optional components, such as salts, whichmay be present in the shampoo composition. This equilibration occursupon incorporation of the pre-formed gel network component with theother components of the shampoo composition and is effectively completewithin about 24 hours after making. Shampoo compositions in which theELD is formed provide hair with improved wet and dry conditioningbenefits. Further, the ELD does not form if the components whichcomprise the gel network component (i.e., the fatty amphiphile and thesecondary surfactant combined with water) are added as individualcomponents together with the other components of the shampoo compositionin one mixing step, and not as a separate cooled pre-formed gel networkcomponent.

The presence of the gel network in the pre-mix and in the final shampoocomposition in the form of the ELD can be confirmed by means known toone of skill in the art, such as X-ray analysis, optical microscopy,electron microscopy, and differential scanning calorimetry. Methods ofX-ray analysis and differential scanning calorimetry are described inthe Examples below.

In an embodiment of the present invention, the weight ratio of the fattyamphiphile to the secondary surfactant in the gel network component isgreater than about 1:9, preferably greater than about 1:5 to about100:1, more preferably greater than about 1:1 to about 50:1, and evenmore preferably greater than about 2:1 to about 10:1.

The shampoo composition of the present invention comprise a gel networkin an amount greater than about 0.1%, preferably from about 1% to about60%, and more preferably from about 5% to about 40%, by weight of theshampoo composition.

1. Fatty Amphiphile

The gel network component of the present invention comprises at leastone fatty amphiphile. As used herein, “fatty amphiphile” refers to acompound having a hydrophobic tail group of R₁ as defined below and ahydrophilic head group which does not make the compound water soluble,wherein the compound also has a net neutral charge at the pH of theshampoo composition. The term “water soluble”, as used herein, meansthat the material is soluble in water in the present composition. Ingeneral, the material should be soluble at 25° C. at a concentration of0.1% by weight of the water solvent, preferably at 1%, more preferablyat 5%, more preferably at 15%.

The fatty amphiphile of the present invention may be characterized as acompound having a Hydrophilic-Lipophilic Balance (“HLB”) of 6 or less.The HLB, as used herein, is the standard HLB according to Griffin, J.Soc. Cosm. Chem., vol. 5, 249 (1954).

The shampoo compositions of the present invention comprise fattyamphiphile as part of the pre-formed dispersed gel network phase in anamount from about 0.05% to about 14%, preferably from about 0.5% toabout 10%, and more preferably from about 1% to about 8%, by weight ofthe shampoo composition.

According to the present invention, suitable fatty amphiphiles, orsuitable mixtures of two or more fatty amphiphiles, have a melting pointof at least about 27° C. The melting point, as used herein, may bemeasured by a standard melting point method as described in U.S.Pharmacopeia, USP-NF General Chapter <741> “Melting range ortemperature”. The melting point of a mixture of two or more materials isdetermined by mixing the two or more materials at a temperature abovethe respective melt points and then allowing the mixture to cool. If theresulting composite is a homogeneous solid below about 27° C., then themixture has a suitable melting point for use in the present invention. Amixture of two or more fatty amphiphiles, wherein the mixture comprisesat least one fatty amphiphile having an individual melting point of lessthan about 27° C., still is suitable for use in the present inventionprovided that the composite melting point of the mixture is at leastabout 27° C.

According to the present invention, suitable fatty amphiphiles have ahydrophobic tail group of R₁. As used herein, R₁ is an alkyl, alkenyl(containing up to 3 double bonds), alkyl aromatic, or branched alkylgroup of C₁₂-C₇₀ length. Non-limiting examples of alkyl, alkenyl, orbranched alkyl groups suitable for the fatty amphiphiles of the presentinvention include lauryl, tridecyl, myristyl, pentadecyl, cetyl,heptadecyl, stearyl, arachidyl, behenyl, undecylenyl, palmitoleyl,oleyl, palmoleyl, linoleyl, linolenyl, arahchidonyl, elaidyl,elaeostearyl, erucyl, isolauryl, isotridecyl, isomyristal,isopentadecyl, petroselinyl, isocetyl, isoheptadecyl, isostearyl,isoarachidyl, isobehnyl, gadoleyl, brassidyl, and technical-grademixture thereof.

As used herein, R₁ also may be a branched alkyl group prepared byalkaline condensation of alcohols to give higher molecular weight,branched isoalcohols. These branched isoalcohols are referred to in theart as Guerbet alcohols.

R₁ may be alkyl, alkenyl or branched carbon chains of vegetable origin,such as wheat germ, sunflower, grape seed, sesame, maize, apricot,castor, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, karite, jojoba, alfalfa, poppy, pumpkinseed,sesame, cucumber, blackcurrant, evening primrose, millet, barley,quinoa, rye, safflower, candlenut, passion flower or musk rose oil, andkarite butter.

Suitable fatty amphiphiles of the present invention also have ahydrophilic head group which does not make the compound water soluble,such as in compounds having an HLB of 6 or less. Non-limiting examplesof classes of compounds having such a hydrophilic head group includefatty alcohols, alkoxylated fatty alcohols, fatty phenols, alkoxylatedfatty phenols, fatty amides, alkyoxylated fatty amides, fatty amines,fatty alkylamidoalkylamines, fatty alkyoxyalted amines, fattycarbamates, fatty amine oxides, fatty acids, alkoxylated fatty acids,fatty diesters, fatty sorbitan esters, fatty sugar esters, methylglucoside esters, fatty glycol esters, mono, di & tri glycerides,polyglycerine fatty esters, alkyl glyceryl ethers, propylene glycolfatty acid esters, cholesterol, ceramides, fatty silicone waxes, fattyglucose amides, and phospholipids.

To form the gel network component of the present invention, individualfatty amphiphile compounds or combinations of two or more differentfatty amphiphile compounds may be selected. The following providesnon-limiting examples of classes of compounds from which one or morefatty amphiphiles suitable for use in the present invention may beselected.

a. Fatty Alcohols/Alkoxylated Fatty Alcohol Ethers

Fatty amphiphiles of the present invention may be selected from fattyalcohol compounds or alkoxylated fatty alcohol ether compounds accordingto the following formula:R₁—(OR₂)_(k)—OHwherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which maybe branched or hydroxy substituted; and k is a number ranging from about0 to about 5.

The fatty alcohols useful herein are those having from about 12 to about60 carbon atoms, preferably from about 16 to about 60 carbon atoms.These fatty alcohols may be straight or branched chain alcohols and maybe saturated or unsaturated. Non-limiting examples of suitable fattyalcohols include cetyl alcohol, stearyl alcohol, arachidyl alcohol,behenyl alcohol, C20-40 alcohols, C30-50 alcohols, C40-60 alcohols, andmixtures thereof.

Suitable alkoxylated fatty alcohol ethers include addition products of 1to 5 mol of ethylene oxide with a linear fatty alcohol having about 12to about 60 carbon atoms, which are all adducts obtainable by the knownindustrial oxyethylation processes. Also suitable are the polyethyleneoxide condensates of alkyl phenols, for example, the condensationproducts of alkyl phenols having an alkyl group containing from about 12to about 60 carbon atoms in either a straight chain or branched chainconfiguration, with ethylene oxide, wherein the ethylene oxide ispresent in amounts equal to from about 1 to about 5 moles of ethyleneoxide per mole of alkyl phenol. Further suitable alkoxylated fattyalcohol ethers include those derived from the condensation of ethyleneoxide with the product resulting from the reaction of propylene oxideand ethylene diamine products.

Non-limiting examples of suitable alkoxylated fatty alcohol ethersinclude steareth-2, beheneth-2, beheneth-5, beheneth-10, C20-40Pareth-3, C20-40 Pareth-10, C30-50 Pareth-3, and C30-50-Pareth-10.

b. Di-Fatty Ethers

Fatty amphiphiles of the present invention may be selected from di-fattyether compounds according to the following formula:R′₁—(OR₂)_(k)—Z—(R₂O)_(l)—R″₁wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k and l each is independently anumber such that the sum (k+l) has a value ranging from 1 to 30; and Zis an ether (i.e., —O—) or an amine (i.e., —NR₂—, wherein R₂ is asdescribed immediately above).

Compounds of the above formula in which Z is an ether (i.e., dialkyloxyethyl ethers) may be prepared by esterification processes, which areknown in the art, of fatty alcohols and fatty alkyl oxyethanols.Compounds of the above formula in which Z is an amine group may beobtained, for example, from triethanolamine by O-alkylation with 2 molof a sulfuric half-ester salt of a C₁₂-C₆₀ fatty alcohol, according to aprocess for the preparation of ether amines described in DE 35 04 242.

Non-limiting examples of suitable di-fatty ether compounds includedicetylstearyl ether, dicetylstearyl dioxyethyl ether, andN,N-bis(2-cetylstearyl-oxyethyl)aminoethanol.

c. Fatty Amides/Fatty Alkanolamides/Fatty Alkoxylated Amides

Fatty amphiphiles of the present invention also may be selected fromfatty amide compounds according to the following formula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; and X and Y are each independently selected fromhydrogen, a C₁-C₄ carbon chain which can be branched or hydroxysubstituted, morpholine, or a C₅-C₅₀ carbon chain bonded via an amide,ester, or ether linkage.

Non-limiting examples of suitable fatty amides, fatty alkanolamides orfatty alkoxylated amides include Cocamide, Cocamide Methyl MEA, CocoylGlutamic Acid, Erucamide, Lauramide, Oleamide, Palmitamide, Stearamide,Stearyl Erucamide, Behenamide DEA, Behenamide MEA, Cocamide DEA,Cocamide MEA, Cocamide MIPA, Hydroxyethyl Stearamide-MIPA, HydroxypropylBisisostearamide MEA, Hydroxypropyl Bislauramide MEA, HydroxystearamideMEA, Isostearamide DEA, Isostearamide MEA, Isostearamide MIPA, LauramideDEA, Lauramide MEA, Lauramide MIPA, Myristamide DEA, Myristamide MEA,Myristamide MIPA, Palmamide DEA, Palmamide MEA, Palmamide MIPA,Palmitamide DEA, Palmitamide MEA, PEG-20 Cocamide MEA, Stearamide AMP,Stearamide DEA, Stearamide DEA-Distearate, Stearamide DIBA-Stearate,Stearamide MEA, Stearamide MEA-Stearate, Stearamide MIPA, PEG-2Cocamide, PEG-3 Cocamide, PEG-4 Cocamide, PEG-5 Cocamide, PEG-6Cocamide, PEG-7 Cocamide, PEG-3 Lauramide, PEG-5 Lauramide, PEG-3Oleamide, PEG-9 Oleamide, PEG-4 Stearamide, PEG-10 Stearamide, PPG-2Cocamide, PPG-2 Hydroxyethyl Cocamide, PPG-2 HydroxyethylCoco/Isostearamide, Ceramide 1, Ceramide 2, Ceramide 3, Ceramide 4, andCeramide 5.

d. Fatty Carbamates

Fatty amphiphiles of the present invention may be selected from fattycarbamate compounds according to the following formula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; and X and Y each is independently selected fromhydrogen, a C₁-C₄ carbon chain which can be branched or hydroxysubstituted, morpholine, or a C₅-C₅₀ carbon chain bonded via an amide,ester, or ether linkage.

Non-limiting examples of suitable fatty carbamates include cetylcarbamate, stearyl carbamate, PEG-2 stearyl carbamate, PEG-4 stearylcarbmate, and behenyl carbamate.

e. Fatty Alkylamido Alkylamines

Fatty amphiphiles of the present invention also may be selected fromfatty alkylamido alkylamine compounds according to the followingformula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; X and Y each is independently selected fromhydrogen, a C₁-C₄ carbon chain which can be branched or hydroxysubstituted, morpholine, or a C₅-C₅₀ carbon chain bonded via an amide,ester, or ether linkage; and n is a number ranging from about 1 to about4.

Non-limiting examples of suitable fatty alkylamido alkylamine compoundsinclude stearamidoethyl diethanolamine, stearamidopropyl morpholine,stearamidopropyl dimethylamine stearate, stearamidopropyl dimethylamine,stearamidoethyl diethylamine, stearamidoethyl diethanolamine,isostearamidomorpholine stearate behenamidopropyldimethylamine,behenamidopropyldiethylamine, behenamidoethyldiethyl-amine,cocamidopropyl dimethylamine behenamidoethyldimethylamine,arachidamidopropyldimethylamine, arachidamido-propyldiethylamine,arachidamidoethyldiethylamine, arachidamidoethyldimethylamine, andmixtures thereof.

f. Fatty Amines/Fatty Alkanolamines/Fatty Alkoxylated Amines

Fatty amphiphiles of the present invention further may be selected fromfatty amine compounds according to the following formula:

wherein R₁ is as described above; and R′₁₅ and R″₁₅ are independentlyhydrogen or a C₁-C₅ carbon chain which can be branched or hydroxysubstituted.

Additionally, fatty amphiphiles of the present invention may be selectedfrom fatty alkoxylated amine compounds according to either one of thefollowing formulas:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; X and Y each is independently hydrogen, a C₁-C₄carbon chain which can be branched or hydroxy substituted, morpholine,or a C₅-C₅₀ carbon chain bonded via amide, ester, or ether linkage; n isa number ranging from about 1 to about 4; and Z is an ether (i.e., —O—)or an amine (i.e., —NH—).

Primary, secondary, and tertiary fatty amines are useful. Suitable fattyalkoxylated amine compounds include addition products of ethylene oxidewith a linear fatty alkylamine having 12 to 60 carbon atoms, all ofwhich are adducts obtainable by known industrial processes and which arecommercially available.

Non-limiting examples of suitable fatty amine and fatty alkoxylatedamine compounds include diethyllauramine, dicocamine, dimethylcocamineamine cetamine, stearamine, oleamine, behenamine, dimethylbehenamineamine, diethylbehenamine, dibehenylamine N-lauryl diethanolamine.TEA-diricinoleate, TEA-lauryl ether, diethylaminoethyl PEG-5 cocoate,diethylaminoethyl PEG-5 laurate, hydroxyethyl isostearyloxyisopropanolamine, PEG-2 cocamine, PEG-5 cocamine, PEG-10 cocamine, PEG-5isodecyloxypropylamine, PEG-2 lauramine, PEG-2 oleamine, PEG-5 oleamine,PEG-10 oleamine, PEG-2 stearamine, PEG-5 stearamine, PEG-10 stearamine,PPG-2 cocamine, PPG-2 hydrogenated tallowamine, PPG-2 tallowamine, andPPG-3 tallow aminopropylamine.

g. Fatty Amine Oxides

Fatty amphiphiles of the present invention also may be selected fromfatty amine oxide compounds according to the following formula:

wherein R₁ is as described above; R₂ and R₃ each is independently aC₁-C₅ carbon chain which can be branched or hydroxy substituted; k and leach is independently a number such that the sum (k+l) has a valueranging from 0 to 10; X and Y each is independently hydrogen, a C₁-C₄carbon chain which can be branched or hydroxy substituted, morpholine,or a C₅-C₅₀ carbon chain bonded via an amide, ester, or ether linkage; Zis an ether (i.e., —O—) or an amide (i.e., —C(O)—NH—) linkage; and n isa number ranging from about 1 to about 4. In accord with knownconvention, the arrow in the above formula is representative of asemi-polar bond.

Non-limiting examples of suitable amine oxide compounds includedimethyl-dodecylamine oxide, oleyldi(2-hydroxyethyl) amine oxide,dimethyltetradecylamine oxide, di(2-hydroxyethyl)-tetradecylamine oxide,dimethylhexadecylamine oxide, behenamine oxide, cocamine oxide,decyltetradecylamine oxide, dihydroxyethyl C12-15 alkoxypropylamineoxide, dihydroxyethyl cocamine oxide, dihydroxyethyl lauramine oxide,dihydroxyethyl stearamine oxide, dihydroxyethyl tallowamine oxide,hydrogenated palm kernel amine oxide, hydrogenated tallowamine oxide,hydroxyethyl hydroxypropyl C12-15 alkoxypropylamine oxide, lauramineoxide, myristamine oxide, myristyl/cetyl amine oxide,oleamidopropylamine oxide, oleamine oxide, palmitamine oxide, PEG-3lauramine oxide, potassium trisphosphonomethylamine oxide, stearamineoxide, and tallowamine oxide.

h. Fatty Acid/Alkoxylated Fatty Acid

Fatty amphiphiles of the present invention also may be selected fromfatty acid or alkoxylated fatty acid compounds according to thefollowing formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; and k is a number ranging from about0 to about 5.

Non-limiting examples of suitable fatty acids and alkoxylated fattyacids include behenic acid, C10-40 hydroxyalkyl acid, C32-36 isoalkylacid coconut acid, erucic acid, hydroxystearic acid, lauric acid,linoleic acid, myristic acid, oleic acid, palmitic acid, PEG-8 behenate,PEG-5 cocoate, PEG-10 cocoate, PEG-2 laurate, PEG-4 laurate PEG-6laurate, PEG-8 laurate, PEG-9 laurate, PEG-10 laurate, PEG-7 oleate,PEG-2 stearate, PEG-3 stearate, PEG-4 stearate, PEG-5 stearate, PEG-6stearate, PEG-7 stearate, PEG-8 stearate, PEG-9 stearate, PEG-10stearate, polyglyceryl-2-PEG-4 stearate, PPG-2 isostearate, and PPG-9laurate.

i. Fatty Esters

Fatty amphiphiles of the present invention may be selected from fattyester compounds according to the following formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k is a number ranging from about 1to about 5; and R₆ is a C₁-C₄₀ carbon chain or an alkylcarbonyl (i.e.,

wherein R₇ is a C₁-C₄₀ carbon chain).

These suitable fatty esters include esters with hydrocarbyl chainsderived from fatty acids or alcohols (e.g., mono-esters, polyhydricalcohol esters, and di- and tri-carboxylic acid esters). The hydrocarbylradicals of the fatty esters hereof may include or have covalentlybonded thereto other compatible functionalities, such as amides andalkoxy moieties (e.g., ethoxy or ether linkages, etc.).

Non-limiting examples of suitable fatty ester compounds includeisopropyl isostearate, hexyl laurate, isohexyl laurate, isohexylpalmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecylstearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate,lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyloleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyladipate.

Fatty amphiphiles of the present invention also may be selected fromother fatty ester compounds according to the following formula:

wherein R′₈, R″₈, and R′″₈ each is independently selected from hydrogen,hydroxy, or a C₁-C₄ carbon chain which can be branched or hydroxysubstituted; k′, k″, and k′″ each is independently a number such thatthe sum (k′+k″+k′″) has a value ranging from 0 to 15; R′₂, R″₂, and R′″₂each is independently selected from a C₁-C₅ carbon chain which can bebranched or hydroxy substituted; and where R′₁₀, R″₁₀, R′″₁₀ each isindependently selected form hydrogen or R₁, where R₁ is as definedabove, provided that at least one of R′₁₀, R″₁₀, and R′″₁₀ is a R1group.

Still other suitable fatty esters are di- and tri-alkyl and alkenylesters of carboxylic acids, such as esters of C₄ to C₈ dicarboxylicacids (e.g., C₁ to C₂₂ esters, preferably C₁ to C₆, of succinic acid,glutaric acid, and adipic acid). Specific non-limiting examples of di-and tri-alkyl and alkenyl esters of carboxylic acids include isocetylstearyol stearate, stearyl citrate, distearyl citrate and tristearylcitrate.

Fatty amphiphiles of the present invention further may be selected fromother fatty ester compounds according to the following formula:

wherein R′₂, R″₂, and R′″₂ each is independently selected from a C₁-C₅carbon chain which can be branched or hydroxy substituted; R′₈, R″₈, andR′″₈ each is independently selected from hydrogen, hydroxy, or C₁-C₄carbon chain which can be branched or hydroxy substituted; k′, k″, andk′″ each is independently a number such that the sum (k′+k″+k′″) has avalue ranging from 0 to 15; and R″₉, R′₉, and R′″₉ each is independentlyselected from hydrogen or alkylcarbonyl (i.e.,

wherein R₁ is as described above), provided that at least one of R′₉,R″₉, and R′″₉ is a

group.

Other suitable fatty esters are those known as polyhydric alcoholesters. Such polyhydric alcohol esters include alkylene glycol esters,such as ethylene glycol mono and di-fatty acid esters, diethylene glycolmono- and di-fatty acid esters, polyethylene glycol mono- and di-fattyacid esters, propylene glycol mono- and di-fatty acid esters,polypropylene glycol monooleate, polypropylene glycol 2000 monostearate,ethoxylated propylene glycol monostearate, glyceryl mono- and di-fattyacid esters, polyglycerol poly-fatty acid esters, ethoxylated glycerylmonostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycoldistearate, polyoxyethylene polyol fatty acid ester.

Still other fatty esters suitable for use in the compositions of thepresent invention are glycerides, including, but not limited to, mono-,di-, and tri-glycerides, preferably mono- and di-glycerides, morepreferably mono-glycerides. For use in the compositions describedherein, the glycerides are preferably the mono-, di-, and tri-esters ofglycerol and long chain carboxylic acids, such as C₁₂ to C₂₂ carboxylicacids. A variety of these types of materials can be obtained fromvegetable and animal fats and oils, such as castor oil, safflower oil,cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocadooil, palm oil, sesame oil, lanolin and soybean oil. Synthetic oilsinclude, but are not limited to, triolein and tristearin glyceryldilaurate.

j. Fatty Phosphorus Compounds

Fatty amphiphiles of the present invention may be selected from fattyphosphorus compounds according to the following formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k is a number ranging from about 0to about 5; and R₅ is hydrogen or a C₁-C₄ carbon chain which can bebranched or hydroxy substituted. In accord with known convention, thearrow in the above formula is representative of a semi-polar bond.

Non-limiting examples of suitable fatty phosphorus compounds includedodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide,tetradecylmethylethylphosphine oxide,3,6,9,-trioxaoctadecyldimethylphosphine oxide, cetyldimethylphosphineoxide, 3-dodecoxy-2-hydroxypropyldi(2-hydroxyethyl) phosphine oxide,stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide,oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide,tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide,dodecyldi(hydroxymethyl)phosphine oxide, dodecyldi(2-hydroxyethyl)phosphine oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide,oleyldimethylphosphine oxide, and 2-hydroxydodecyldimethylphosphineoxide.

k. Fatty Sorbitan Derivatives

Fatty amphiphiles of the present invention also may be selected fromfatty sorbitan derivative compounds according to the following formula:

wherein R′₂, R″₂, R′″₂, and R″″₂ each is independently a C₁-C₅ carbonchain which can be branched or hydroxy substituted; R′₉, R″₉, R′″₉, andR″″₉ each is independently hydrogen or alkylcarbonyl (i.e.,

wherein R₁ is as described above), provided that at least one of R′₉,R″₉, R′″₉, and R″″₉ is a

group; and k′, k″, k′″, and k″″ each is independently a number such thatthe sum (k′+k″+k′″+k″″) has a value ranging from 0 to 20.

Non-limiting examples of suitable fatty sorbitan derivatives includePEG-20 sorbitan cocoate, PEG-2 sorbitan isostearate, PEG-5 sorbitanisostearate, PEG-20 sorbitan isostearate, PEG-10 sorbitan laurate, PEG-3sorbitan oleate, PEG-6 sorbitan oleate, PEG-20 sorbitan oleate, PEG-3sorbitan stearate, PEG-4 sorbitan stearate, PEG-6 sorbitan stearate,PEG-4 sorbitan triisostearate, PEG-20 sorbitan triisostearate, PEG-2sorbitan trioleate, PEG-3 sorbitan tristearate, polyglyceryl-2 sorbitantetraethylhexanoate, sorbitan caprylate, sorbitan cocoate, sorbitandiisostearate, sorbitan dioleate, sorbitan distearate, sorbitanisostearate, sorbitan laurate, sorbitan oleate, sorbitan olivate,sorbitan palmitate, sorbitan sesquiisostearate, sorbitan sesquioleate,sorbitan sesquistearate, sorbitan stearate, sorbitan triisostearate,sorbitan trioleate, sorbitan tristearate, and sorbitan undecylenate.

1. Sucrose Polyesters

Fatty amphiphiles of the present invention may be selected from sucrosepolyester compounds according to the following formula:

wherein R′₉, R″₉, R′″₉, R″″₉, R′″″₉, R″″″₉, R′″″″₉, and R″″″″₉ each ishydrogen or alkylcarbonyl (i.e.,

wherein R₁ is as described above), provided that at least one of R′₉,R″₉, R′″₉, R″″₉, R′″″₉, R″″″₉, R′″″″₉, and R″″″″₉ is a

group.

Non-limiting examples of suitable sucrose polyester compounds includeSucrose Cocoate, Sucrose Dilaurate, Sucrose Distearate, SucroseHexaerucate, Sucrose Hexaoleate/Hexapalmitate/Hexastearate, SucroseHexapalmitate, Sucrose Laurate, Sucrose Mortierellate, SucroseMyristate, Sucrose Octaacetate, Sucrose Oleate, Sucrose Palmitate,Sucrose Pentaerucate, Sucrose Polybehenate, Sucrose Polycottonseedate,Sucrose Polylaurate, Sucrose Polylinoleate, Sucrose Polyoleate, SucrosePolypalmate, Sucrose Polysoyate, Sucrose Polystearate, SucroseRicinoleate, Sucrose Stearate, Sucrose Tetraisostearate, SucroseTetrastearate Triacetate, Sucrose Tribehenate, and Sucrose Tristearate.

m. Alkyl Sulfoxides

Fatty amphiphiles of the present invention further may be selected fromalkyl sulfoxide compounds according to the following formula:

wherein R₁ is as described above; R₂ is a C₁-C₅ carbon chain which canbe branched or hydroxy substituted; k is a number ranging from about 0to about 10; and X and Y each is independently selected from hydrogen ora C₁-C₄ carbon chain which can be branched or hydroxy substituted.

Non-limiting examples of suitable alkyl sulfoxide compounds includeoctadecyl methyl sulfoxide, 2-ketotridecyl methyl sulfoxide,3,6,9,-trioxaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methylsulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetradecyl methyl sulfoxide,3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide,and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

2. Secondary Surfactant

The gel network component of the present invention also comprises asecondary surfactant. As used herein, “secondary surfactant” refers toone or more surfactants which are combined with the fatty amphiphile andwater to form the gel network of the present invention as a pre-mixseparate from the other components of the shampoo composition. Thesecondary surfactant is separate from and in addition to the detersivesurfactant component of the shampoo composition. However, the secondarysurfactant may be the same or different type of surfactant orsurfactants as that or those selected for the detersive surfactantcomponent described above.

The shampoo compositions of the present invention comprise secondarysurfactant as part of the pre-formed dispersed gel network phase in anamount from about 0.01% to about 15%, preferably from about 0.1% toabout 10%, and more preferably from about 0.3% to about 5%, by weight ofthe shampoo composition.

As described above, for use in the present invention, the weight ratioof the fatty amphiphile to the secondary surfactant is greater thanabout 1:9, preferably greater than about 1:5 to about 100:1, morepreferably greater than about 1:1 to about 50:1, and even morepreferably greater than about 2:1 to about 10:1.

Suitable secondary surfactants include anionic, zwitterionic,amphoteric, cationic, and nonionic surfactants as generally describedabove in the Detersive Surfactant section.

Preferred anionic surfactants for use as secondary surfactants of thepresent invention include ammonium lauryl sulfate, ammonium laurethsulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate,triethanolamine lauryl sulfate, triethanolamine laureth sulfate,monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate,diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauricmonoglyceride sodium sulfate, sodium lauryl sulfate, sodium laurethsulfate, potassium lauryl sulfate, potassium laureth sulfate, sodiumlauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoylsarcosine, ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodiumcocoyl sulfate, sodium lauroyl sulfate, potassium cocoyl sulfate,potassium lauryl sulfate, triethanolamine lauryl sulfate,triethanolamine lauryl sulfate, monoethanolamine cocoyl sulfate,monoethanolamine lauryl sulfate, sodium tridecyl benzene sulfonate,sodium dodecyl benzene sulfonate, sodium cocoyl isethionate, andcombinations thereof.

Cationic surfactants suitable for use as secondary surfactants of thepresent invention include quaternary ammonium salts or amido-amineshaving at least one fatty chain containing at least about 8 carbon atomsand mixture thereof.

Suitable quaternary ammonium salts have the following general formula:N⁺(R₁R₂R₃R₄)X⁻wherein R₁ is selected from linear and branched radicals comprising fromabout 8 to about 12 carbon atoms; R₂ is selected from linear andbranched radicals comprising from about 8 to 12 carbon atoms or the samegroup as radicals R₃ and R₄; R₃ and R₄ are independently selected fromlinear and branched aliphatic radicals comprising from about 1 to about4 carbon atoms, and aromatic radicals such as aryl and alkylaryl,wherein the aliphatic radicals may comprise at least one hetero atomsuch as oxygen, nitrogen, sulphur, and halogens, and the aliphaticradicals are chosen, for example, from alkyl, alkoxy, and alkylamideradicals; and X— is an anion selected from halides such as chloride,bromide, and iodide, (C₂-C₆)alkyl sulphates, such as methyl sulphate,phosphates, alkyl, and alkylaryl sulphonates, and anions derived fromorganic acids, such as acetate and lactate.

Non-limiting examples of such suitable cationic surfactants includecetrimonium chloride, stearimonium chloride, behentrimonium chloride,behentrimonium methosulfate, behenamidopropyltrimonium methosulfate,stearamidopropyltrimonium chloride, arachidtrimonium chloride,distearyldimonium chloride, dicetyldimonium chloride, tricetylmoniumchloride, oleamidopropyl dimethylamine, linoleamidopropyl dimethylamine,isostearamidopropyl dimethylamine, oleyl hydroxyethyl imidazoline, andmixtures thereof.

Suitable amido-amine cationic surfactants have the following generalformula:R′₁—CONH(CH₂)nNR′₂R′₃wherein R′₁ is selected from linear and branched radicals comprisingabout 8 to about 12 carbon atoms; R′₂ and R′₃ are independently selectedfrom hydrogen, linear and branched aliphatic radicals comprising fromabout 1 to about 4 carbon atoms, and aromatic radicals such as aryl andalkylaryl, wherein the aliphatic radicals may comprise at least onehetero atom such as oxygen, nitrogen, sulphur, and halogens, and thealiphatic radicals are chosen, for example, from alkyl, alkoxy andalkylamide radicals; and n is an integer from about 1 to about 4.

Non-limiting examples of such suitable amido-amines includestearamidopropyldimethylamine, behenamidopropyldimethylamine,behenamidopropyldiethylamine, behenamidoethyldiethyl-amine,behenamidoethyldimethylamine, arachidamidopropyldimethylamine,arachidamido-propyldiethylamine, arachidamidoethyldiethylamine,arachidamidoethyldimethylamine, and mixtures thereof.

Suitable nonionic surfactants include nonionic surfactants having an HLBof 7 or more and comprising one or more polyethyleneoxide chains whereineach polyethyleneoxide chain contains on average at least about 5ethylene oxide units.

Nonionic surfactants comprising one or more polyethyleneoxide chainwherein each polyethyleneoxide chain contains on average at least about5 ethylene oxide units include polyoxyethylene alkyl ethers,polyethyleneglycol fatty acid esters, polyoxyethylene castor oil,polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty amidesand their monoethanolamine and diethanolamine derivatives, andpolyethoxylated fatty amines, with a number of ethylene oxide groups ofat least about 5, and mixtures thereof.

Among preferred nonionic surfactants comprising one or morepolyethyleneoxide chain include polyoxyethylene alkyl ethers having atleast about 5, preferably from about 10 to 20, ethylene oxide units.Examples of such nonionic surfactants are steareth-10 and steareth-15.

Also suitable for use as nonionic surfactants are nonionic surfactantshaving an HLB of 7 or more which are free of polyethyleneoxide chains.Nonionic surfactants free of polyethyleneoxide chains includepolyglycerolated fatty acids, polyglycerolated fatty amides,polyglycerolated alkyl phenols, polyglycerolated α-diols,polyglycerolated alcohols, alkyl polyglucosides, and sugar esters.Preferably, suitable nonionic surfactants free of polyethyleneoxidechains are selected from alkyl polyglucosides, sugar esters,polyglyceryl fatty acid esters, alkyl polyglyceryl ethers, and mixturesthereof.

Suitable secondary surfactants of the present invention also includeso-called gemini surfactants. Gemini surfactants are generally describedby F. M. Menger and C. A. Littau, “Gemini Surfactants: A New Class ofSelf-Assembling Molecules”, J. Am. Chem. Soc. 1993, 115, 10083-10090;and by B. S. Sekon, “Gemini (dimeric) Surfactants: The Two FacedMolecules”, Resonance, 42-49 (March 2004). Examples of suitable geminisurfactants are described in U.S. Pat. Nos. 5,922,671; 6,204,297;6,358,914; 6,710,022; 6,777,384; 6,794,345; and 6,797,687.

More than one surfactant of the above specified types may be used forthe secondary surfactant of the present invention.

3. Water or Suitable Solvents

The gel network component of the present invention also comprises wateror suitable solvents. The water or suitable solvent and the secondarysurfactant together contribute to the swelling of the fatty amphiphile.This, in turn, leads to the formation and the stability of the gelnetwork. As used herein, the term “suitable solvent” refers to anysolvent which can be used in the place of or in combination with waterin the formation of the gel network of the present invention.

The shampoo compositions of the present invention comprise water orsuitable solvents as part of the pre-formed dispersed gel network phasein an amount suitable to achieve a gel network when combined with fattyamphiphile and secondary surfactant according to the present invention.

In a preferred embodiment, the shampoo compositions of the presentinvention comprise as part of the pre-formed dispersed gel network phaseat least about 0.05% of water or a suitable solvent, by weight of theshampoo composition.

In another embodiment of the present invention, the shampoo compositionscomprise water or a suitable solvent as part of the pre-formed dispersedgel network phase is an amount relative to the amount of fattyamphiphile at a weight ratio of at least about 1:1.

C. Aqueous Carrier

The shampoo compositions of the present invention comprise an aqueouscarrier. Typically, the compositions of the present invention are in theform of pourable liquids (under ambient conditions). The compositions,therefore, comprise an aqueous carrier at a level of from about 20% toabout 95%, preferably from about 60% to about 85%, by weight of thecompositions. The aqueous carrier may comprise water, or a misciblemixture of water and organic solvent, but preferably comprises waterwith minimal or no significant concentrations of organic solvent, exceptas otherwise incidentally incorporated into the composition as minoringredients of other essential or optional components.

D. Additional Components

The compositions of the present invention may further comprise one ormore optional components known for use in hair care or personal careproducts, provided that the optional components are physically andchemically compatible with the essential components described herein, ordo not otherwise unduly impair product stability, aesthetics orperformance. Individual concentrations of such optional components mayrange from about 0.001% to about 10% by weight of the compositions.

Non-limiting examples of optional components for use in the compositioninclude cationic polymers, conditioning agents (hydrocarbon oils, fattyesters, silicones), anti-dandruff agents, suspending agents, viscositymodifiers, dyes, nonvolatile solvents or diluents (water soluble andinsoluble), pearlescent aids, foam boosters, additional surfactants ornonionic cosurfactants, pediculocides, pH adjusting agents, perfumes,preservatives, chelants, proteins, skin active agents, sunscreens, UVabsorbers, and vitamins.

1. Deposition Aid

The shampoo compositions of the present invention may include adeposition aid. The deposition aid is included to effectively enhancedeposition of the gel network component. The deposition aid can compriseany material that enhances the deposition of the gel network from theshampoo onto the hair and/or scalp.

The concentration of the deposition aid in the shampoo compositionshould be sufficient to effectively enhance the deposition of the gelnetwork component and ranges from about 0.05% to about 5%, preferablyfrom about 0.075% to about 2.5%, more preferably from about 0.1% toabout 1.0%, by weight of the shampoo composition.

In one embodiment of the present invention, the deposition aid is acationic polymer. Preferred cationic polymers will have cationic chargedensities of at least about 0.9 meq/g, preferably at least about 1.2meq/g, more preferably at least about 1.5 meq/g, but also preferablyless than about 7 meq/g, more preferably less than about 5 meq/g, at thepH of intended use of the composition. The pH will generally range fromabout pH 3 to about pH 9, preferably between about pH 4 and about pH 8.The “cationic charge density” of a polymer, as that term is used herein,refers to the ratio of the number of positive charges on the polymer tothe molecular weight of the polymer. The average molecular weight ofsuch suitable cationic polymers will generally be between about 10,000and 10 million, preferably between about 50,000 and about 5 million,more preferably between about 100,000 and about 3 million.

Suitable cationic polymers for use in the compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. The cationicprotonated amines can be primary, secondary, or tertiary amines(preferably secondary or tertiary), depending upon the particularspecies and the selected pH of the composition. Any anionic counterionscan be used in association with the cationic polymers so long as thepolymers remain soluble in water, in the composition, or in a coacervatephase of the composition, and so long as the counterions are physicallyand chemically compatible with the essential components of thecomposition or do not otherwise unduly impair product performance,stability or aesthetics. Non limiting examples of such counterionsinclude halides (e.g., chloride, fluoride, bromide, iodide), sulfate andmethylsulfate.

Non-limiting examples of such polymers are described in the CTFACosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley,and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C. (1982)).

Non-limiting examples of suitable cationic polymers include copolymersof vinyl monomers having cationic protonated amine or quaternaryammonium functionalities with water soluble spacer monomers such asacrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl anddialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinylcaprolactone or vinyl pyrrolidone.

Suitable cationic protonated amino and quaternary ammonium monomers, forinclusion in the cationic polymers of the composition herein, includevinyl compounds substituted with dialkylaminoalkyl acrylate,dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate,monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammoniumsalt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammoniumsalts, and vinyl quaternary ammonium monomers having cyclic cationicnitrogen-containing rings such as pyridinium, imidazolium, andquaternized pyrrolidone, e.g., alkyl vinyl imidazolium, alkyl vinylpyridinium, alkyl vinyl pyrrolidone salts.

Other suitable cationic polymers for use in the compositions includecopolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt(e.g., chloride salt) (referred to in the industry by the Cosmetic,Toiletry, and Fragrance Association, “CTFA”, as Polyquaternium-16);copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate(referred to in the industry by CTFA as Polyquaternium-11); cationicdiallyl quaternary ammonium-containing polymers, including, for example,dimethyldiallylammonium chloride homopolymer, copolymers of acrylamideand dimethyldiallylammonium chloride (referred to in the industry byCTFA as Polyquaternium 6 and Polyquaternium 7, respectively); amphotericcopolymers of acrylic acid including copolymers of acrylic acid anddimethyldiallylammonium chloride (referred to in the industry by CTFA asPolyquaternium 22), terpolymers of acrylic acid withdimethyldiallylammonium chloride and acrylamide (referred to in theindustry by CTFA as Polyquaternium 39), and terpolymers of acrylic acidwith methacrylamidopropyl trimethylammonium chloride and methylacrylate(referred to in the industry by CTFA as Polyquaternium 47). Preferredcationic substituted monomers are the cationic substituteddialkylaminoalkyl acrylamides, dialkylaminoalkyl methacrylamides, andcombinations thereof. These preferred monomers conform the to theformula

wherein R¹ is hydrogen, methyl or ethyl; each of R², R³ and R⁴ areindependently hydrogen or a short chain alkyl having from about 1 toabout 8 carbon atoms, preferably from about 1 to about 5 carbon atoms,more preferably from about 1 to about 2 carbon atoms; n is an integerhaving a value of from about 1 to about 8, preferably from about 1 toabout 4; and X is a counterion. The nitrogen attached to R₂, R₃ and R₄may be a protonated amine (primary, secondary or tertiary), but ispreferably a quaternary ammonium wherein each of R², R³ and R⁴ are alkylgroups a non limiting example of which is polymethyacrylamidopropyltrimonium chloride, available under the trade name Polycare 133, fromRhone-Poulenc, Cranberry, N.J., U.S.A. Also preferred are copolymers ofthe above cationic monomer with nonionic monomers such that the chargedensity of the total copolymer is from about 2.0 meq/g to about 4.5meq/g.

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, such as cationic cellulose derivatives andcationic starch derivatives. Suitable cationic polysaccharide polymersinclude those which conform to the formula

wherein A is an anhydroglucose residual group, such as a starch orcellulose anhydroglucose residual; R is an alkylene oxyalkylene,polyoxyalkylene, or hydroxyalkylene group, or combination thereof; R1,R2, and R3 independently are alkyl, aryl, alkylaryl, arylalkyl,alkoxyalkyl, or alkoxyaryl groups, each group containing up to about 18carbon atoms, and the total number of carbon atoms for each cationicmoiety (i.e., the sum of carbon atoms in R1, R2 and R3) preferably beingabout 20 or less; and X is an anionic counterion as described inhereinbefore.

Preferred cationic cellulose polymers are salts of hydroxyethylcellulose reacted with trimethyl ammonium substituted epoxide, referredto in the industry (CTFA) as Polyquaternium 10 and available fromAmerchol Corp. (Edison, N.J., USA) in their Polymer LR, JR, and KGseries of polymers. Other suitable types of cationic cellulose includethe polymeric quaternary ammonium salts of hydroxyethyl cellulosereacted with lauryl dimethyl ammonium-substituted epoxide referred to inthe industry (CTFA) as Polyquaternium 24. These materials are availablefrom Amerchol Corp. under the tradename Polymer LM-200.

Other suitable cationic polymers include cationic guar gum derivatives,such as guar hydroxypropyltrimonium chloride, specific examples of whichinclude the Jaguar series commercially avaialable from Rhone-PoulencIncorporated and the N-Hance series commercially available from AqualonDivision of Hercules, Inc. Other suitable cationic polymers includequaternary nitrogen-containing cellulose ethers, some examples of whichare described in U.S. Pat. No. 3,962,418. Other suitable cationicpolymers include copolymers of etherified cellulose, guar and starch,some examples of which are described in U.S. Pat. No. 3,958,581. Whenused, the cationic polymers herein are either soluble in the compositionor are soluble in a complex coacervate phase in the composition formedby the cationic polymer and the anionic, amphoteric and/or zwitterionicdetersive surfactant component described hereinbefore. Complexcoacervates of the cationic polymer can also be formed with othercharged materials in the composition.

Techniques for analysis of formation of complex coacervates are known inthe art. For example, microscopic analyses of the compositions, at anychosen stage of dilution, can be utilized to identify whether acoacervate phase has formed. Such coacervate phase will be identifiableas an additional emulsified phase in the composition. The use of dyescan aid in distinguishing the coacervate phase from other insolublephases dispersed in the composition.

2. Dispersed Particles

The composition of the present invention may include dispersedparticles. Particles useful in the present invention can be inorganic,synthetic, or semi-synthetic in origin. If present in the compositionsof the present invention, dispersed particles are incorporated in anamount from about 0.025% to about 20%, preferably from about 0.05% toabout 10%, more preferably from about 0.1% to about 5%, even morepreferably from about 0.25% to about 3%, and yet more preferably fromabout 0.5% to about 2%, by weight of the composition.

3. Nonionic Polymers

Polyalkylene glycols having a molecular weight of more than about 1000are useful herein. Useful are those having the following generalformula:

wherein R⁹⁵ is selected from the group consisting of H, methyl, andmixtures thereof. Polyethylene glycol polymers useful herein are PEG-2M(also known as Polyox WSR® N-10, which is available from Union Carbideand as PEG-2,000); PEG-5M (also known as Polyox WSR® N-35 and PolyoxWSR® N-80, available from Union Carbide and as PEG-5,000 andPolyethylene Glycol 300,000); PEG-7M (also known as Polyox WSR® N-750available from Union Carbide); PEG-9M (also known as Polyox WSR® N-3333available from Union Carbide); and PEG-14 M (also known as Polyox WSR®N-3000 available from Union Carbide).

4. Conditioning Agents

The compositions of the present invention may also comprise one or moreconditioning agents. Conditioning agents include materials which areused to give a particular conditioning benefit to hair and/or skin. Theconditioning agents useful in the compositions of the present inventiontypically comprise a water-insoluble, water-dispersible, non-volatile,liquid that forms emulsified, liquid particles. Suitable conditioningagents for use in the composition are those conditioning agentscharacterized generally as silicones (e.g., silicone oils, cationicsilicones, silicone gums, high refractive silicones, and siliconeresins), organic conditioning oils (e.g., hydrocarbon oils, polyolefins,and fatty esters) or combinations thereof, or those conditioning agentswhich otherwise form liquid, dispersed particles in the aqueoussurfactant matrix.

One or more conditioning agents are present from about 0.01% to about10%, preferably from about 0.1% to about 8%, more preferably from about0.2% to about 4%, by weight of the composition.

The conditioning agents may be present in the dispersed gel networkphase or may be added to the final shampoo composition as a separatecomponent.

a. Silicones

The conditioning agents of the compositions of the present invention maybe a water-insoluble silicone conditioning agent. The siliconeconditioning agent may comprise volatile silicone, non-volatilesilicone, or combinations thereof. The silicone conditioning agentparticles may comprise a silicone fluid conditioning agent and may alsocomprise other ingredients, such as a silicone resin to improve siliconefluid deposition efficiency or enhance glossiness of the hair.

Non-limiting examples of suitable silicone conditioning agents, andoptional suspending agents for the silicone, are described in U.S.Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat. No.5,106,609. The silicone conditioning agents for use in the compositionsof the present invention preferably have a viscosity, as measured at 25°C., from about 20 to about 2,000,000 centistokes (“csk”), morepreferably from about 1,000 to about 1,800,000 csk, even more preferablyfrom about 10,000 to about 1,500,000 csk, more preferably from about20,000 to about 1,000,000 csk.

In an opaque composition embodiment of the present invention, thepersonal care composition comprises a non-volatile silicone oil having aparticle size as measured in the personal care composition from about 1μm to about 50 μm. In an embodiment of the present invention for smallparticle application to the hair, the personal care compositioncomprises a non-volatile silicone oil having a particle size as measuredin the personal care composition from about 100 nm to about 1 μm. Asubstantially clear composition embodiment of the present inventioncomprises a non-volatile silicone oil having a particle size as measuredin the personal care composition of less than about 100 nm.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, are foundin Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989).

Silicone fluids suitable for use in the compositions of the presentinvention are disclosed in U.S. Pat. No. 2,826,551, U.S. Pat. No.3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433, andSilicon Compounds, Petrarch Systems, Inc. (1984).

i. Silicone Oils

Silicone fluids include silicone oils, which are flowable siliconematerials having a viscosity, as measured at 25° C., less than 1,000,000csk, preferably from about 5 csk to about 1,000,000 csk, more preferablyfrom about 100 csk to about 600,000 csk. Suitable silicone oils for usein the compositions of the present invention include polyalkylsiloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyethersiloxane copolymers, and mixtures thereof. Other insoluble, non-volatilesilicone fluids having hair conditioning properties may also be used.

Silicone oils include polyalkyl or polyaryl siloxanes which conform tothe following Formula (I):

wherein R is aliphatic, preferably alkyl or alkenyl, or aryl, R can besubstituted or unsubstituted, and x is an integer from 1 to about 8,000.Suitable R groups for use in the compositions of the present inventioninclude, but are not limited to: alkoxy, aryloxy, alkaryl, arylalkyl,arylalkenyl, alkamino, and ether-substituted, hydroxyl-substituted, andhalogen-substituted aliphatic and aryl groups. Suitable R groups alsoinclude cationic amines and quaternary ammonium groups.

Preferred alkyl and alkenyl substituents are C₁ to C₅ alkyls andalkenyls, more preferably from C₁ to C₄, more preferably from C₁ to C₂.The aliphatic portions of other alkyl-, alkenyl-, or alkynyl-containinggroups (such as alkoxy, alkaryl, and alkamino) can be straight orbranched chains, and are preferably from C₁ to C₅, more preferably fromC₁ to C₄, even more preferably from C₁ to C₃, more preferably from C₁ toC₂. As discussed above, the R substituents can also contain aminofunctionalities (e.g. alkamino groups), which can be primary, secondaryor tertiary amines or quaternary ammonium. These include mono-, di- andtri-alkylamino and alkoxyamino groups, wherein the aliphatic portionchain length is preferably as described herein.

ii. Amino and Cationic Silicones

Amino and/or cationic silicone fluids suitable for use in thecompositions of the present invention include, but are not limited to,those which conform to the general formula (II):(R₁)_(a)G_(3-a)-Si—(—OSiG₂)_(n)-(—OSiG_(b)(R₁)_(2-b))_(m)—O—SiG_(3-a)(R₁)_(a)wherein G is hydrogen, phenyl, hydroxy, or C₁-C₈ alkyl, preferablymethyl; a is 0 or an integer having a value from 1 to 3, preferably 0; bis 0 or 1, preferably 1; n is a number from 0 to 1,999, preferably from49 to 499; m is an integer from 1 to 2,000, preferably from 1 to 10; thesum of n and m is a number from 1 to 2,000, preferably from 50 to 500;R₁ is a monovalent radical conforming to the general formula CqH_(2q)L,wherein q is an integer having a value from 2 to 8 and L is selectedfrom the following groups:

-   -   —N(R₂)CH₂—CH₂—N(R₂)₂    -   —N(R₂)₂    -   —N(R₂)₃A⁻    -   —N(R₂)CH₂—CH₂—NR₂H₂A⁻        wherein R₂ is hydrogen, phenyl, benzyl, or a saturated        hydrocarbon radical, preferably an alkyl radical from about C₁        to about C₂₀, and A⁻ is a halide ion.

An especially preferred amino silicone corresponding to formula (II) isthe polymer known as “trimethylsilylamodimethicone”, which is shownbelow in formula (III):

Other silicone cationic polymers which may be used in the compositionsof the present invention are represented by the general formula (IV):

wherein R³ is a monovalent hydrocarbon radical from C₁ to C₁₈,preferably an alkyl or alkenyl radical, such as methyl; R₄ is ahydrocarbon radical, preferably a C₁ to C₁₈ alkylene radical or a C₁₀ toC₁₈ alkyleneoxy radical, more preferably a C₁ to C₈ alkyleneoxy radical;Q⁻ is a halide ion, preferably chloride; r is an average statisticalvalue from 2 to 20, preferably from 2 to 8; s is an average statisticalvalue from 20 to 200, preferably from 20 to 50. A preferred polymer ofthis class is known as UCARE SILICONE ALE 56™, available from UnionCarbide.

iii. Silicone Gums

Other silicone fluids suitable for use in the compositions of thepresent invention are the water-insoluble silicone gums. These gums arepolyorganosiloxane materials having a viscosity, as measured at 25° C.,of greater than or equal to 1,000,000 csk. Silicone gums are describedin U.S. Pat. No. 4,152,416; Noll and Walter, Chemistry and Technology ofSilicones, New York: Academic Press (1968); and in General ElectricSilicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76.Specific non-limiting examples of silicone gums for use in thecompositions of the present invention include polydimethylsiloxane,(polydimethylsiloxane) (methylvinylsiloxane) copolymer,poly(dimethylsiloxane) (diphenyl siloxane)(methylvinylsiloxane)copolymer and mixtures thereof.

iv. High Refractive Index Silicones

Other non-volatile, insoluble silicone fluid conditioning agents thatare suitable for use in the compositions of the present invention arethose known as “high refractive index silicones,” having a refractiveindex of at least about 1.46, preferably at least about 1.48, morepreferably at least about 1.52, more preferably at least about 1.55. Therefractive index of the polysiloxane fluid will generally be less thanabout 1.70, typically less than about 1.60. In this context,polysiloxane “fluid” includes oils as well as gums.

The high refractive index polysiloxane fluid includes those representedby general Formula (I) above, as well as cyclic polysiloxanes such asthose represented by Formula (V) below:

wherein R is as defined above for Formula (I), and n is a number fromabout 3 to about 7, preferably from about 3 to about 5.

The high refractive index polysiloxane fluids contain an amount ofaryl-containing R substituents sufficient to increase the refractiveindex to the desired level, which is described herein. Additionally, Rand n must be selected so that the material is non-volatile.

Aryl-containing substituents include those which contain alicyclic andheterocyclic five and six member aryl rings and those which containfused five or six member rings. The aryl rings themselves can besubstituted or unsubstituted.

Generally, the high refractive index polysiloxane fluids will have adegree of aryl-containing substituents of at least about 15%, preferablyat least about 20%, more preferably at least about 25%, even morepreferably at least about 35%, more preferably at least about 50%.Typically, the degree of aryl substitution will be less than about 90%,more generally less than about 85%, preferably from about 55% to about80%.

Preferred high refractive index polysiloxane fluids have a combinationof phenyl or phenyl derivative substituents (more preferably phenyl),with alkyl substituents, preferably C₁-C₄ alkyl (more preferablymethyl), hydroxy, or C₁-C₄ alkylamino (especially —R¹NHR²NH2 whereineach R¹ and R² independently is a C₁-C₃ alkyl, alkenyl, and/or alkoxy).

When high refractive index silicones are used in the compositions of thepresent invention, they are preferably used in solution with a spreadingagent, such as a silicone resin or a surfactant, to reduce the surfacetension by a sufficient amount to enhance spreading and thereby enhancethe glossiness (subsequent to drying) of hair treated with thecompositions.

Silicone fluids suitable for use in the compositions of the presentinvention are disclosed in U.S. Pat. No. 2,826,551, U.S. Pat. No.3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433, andSilicon Compounds, Petrarch Systems, Inc. (1984).

v. Silicone Resins

Silicone resins may be included in the silicone conditioning agent ofthe compositions of the present invention. These resins are highlycross-linked polymeric siloxane systems. The cross-linking is introducedthrough the incorporation of trifunctional and tetrafunctional silaneswith monofunctional or difunctional, or both, silanes during manufactureof the silicone resin.

Silicone materials and silicone resins in particular, can convenientlybe identified according to a shorthand nomenclature system known tothose of ordinary skill in the art as “MDTQ” nomenclature. Under thissystem, the silicone is described according to presence of varioussiloxane monomer units which make up the silicone. Briefly, the symbol Mdenotes the monofunctional unit (CH₃)₃SiO_(0.5); D denotes thedifunctional unit (CH₃)₂SiO; T denotes the trifunctional unit(CH₃)SiO_(1.5); and Q denotes the quadra- or tetra-functional unit SiO₂.Primes of the unit symbols (e.g. M′, D′, T′, and Q′) denote substituentsother than methyl, and must be specifically defined for each occurrence.

Preferred silicone resins for use in the compositions of the presentinvention include, but are not limited to MQ, MT, MTQ, MDT and MDTQresins. Methyl is a preferred silicone substituent. Especially preferredsilicone resins are MQ resins, wherein the M:Q ratio is from about0.5:1.0 to about 1.5:1.0 and the average molecular weight of thesilicone resin is from about 1000 to about 10,000.

The weight ratio of the non-volatile silicone fluid, having refractiveindex below 1.46, to the silicone resin component, when used, ispreferably from about 4:1 to about 400:1, more preferably from about 9:1to about 200:1, more preferably from about 19:1 to about 100:1,particularly when the silicone fluid component is a polydimethylsiloxanefluid or a mixture of polydimethylsiloxane fluid andpolydimethylsiloxane gum as described herein. Insofar as the siliconeresin forms a part of the same phase in the compositions hereof as thesilicone fluid, i.e. the conditioning active, the sum of the fluid andresin should be included in determining the level of siliconeconditioning agent in the composition.

b. Organic Conditioning Oils

The conditioning component of the compositions of the present inventionmay also comprise from about 0.05% to about 3%, by weight of thecomposition, preferably from about 0.08% to about 1.5%, more preferablyfrom about 0.1% to about 1%, of at least one organic conditioning oil asthe conditioning agent, either alone or in combination with otherconditioning agents, such as the silicones described above.

i. Hydrocarbon Oils

Suitable organic conditioning oils for use as conditioning agents in thecompositions of the present invention include, but are not limited to,hydrocarbon oils having at least about 10 carbon atoms, such as cyclichydrocarbons, straight chain aliphatic hydrocarbons (saturated orunsaturated), and branched chain aliphatic hydrocarbons (saturated orunsaturated), including polymers and mixtures thereof. Straight chainhydrocarbon oils preferably are from about C₁₂ to about C₁₉. Branchedchain hydrocarbon oils, including hydrocarbon polymers, typically willcontain more than 19 carbon atoms.

Specific non-limiting examples of these hydrocarbon oils includeparaffin oil, mineral oil, saturated and unsaturated dodecane, saturatedand unsaturated tridecane, saturated and unsaturated tetradecane,saturated and unsaturated pentadecane, saturated and unsaturatedhexadecane, polybutene, polydecene, and mixtures thereof. Branched-chainisomers of these compounds, as well as of higher chain lengthhydrocarbons, can also be used, examples of which include highlybranched, saturated or unsaturated, alkanes such as thepermethyl-substituted isomers, e.g., the permethyl-substituted isomersof hexadecane and eicosane, such as 2, 2, 4, 4, 6, 6, 8,8-dimethyl-10-methylundecane and 2, 2, 4, 4, 6,6-dimethyl-8-methylnonane, available from Permethyl Corporation.Hydrocarbon polymers such as polybutene and polydecene. A preferredhydrocarbon polymer is polybutene, such as the copolymer of isobutyleneand butene. A commercially available material of this type is L-14polybutene from Amoco Chemical Corporation.

ii. Polyolefins

Organic conditioning oils for use in the compositions of the presentinvention can also include liquid polyolefins, more preferably liquidpoly-α-olefins, more preferably hydrogenated liquid poly-α-olefins.Polyolefins for use herein are prepared by polymerization of C₄ to aboutC₁₄ olefenic monomers, preferably from about C₆ to about C₁₂.

Non-limiting examples of olefenic monomers for use in preparing thepolyolefin liquids herein include ethylene, propylene, 1-butene,1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,branched chain isomers such as 4-methyl-1-pentene, and mixtures thereof.Also suitable for preparing the polyolefin liquids are olefin-containingrefinery feedstocks or effluents. Preferred hydrogenated α-olefinmonomers include, but are not limited to: 1-hexene to 1-hexadecenes,1-octene to 1-tetradecene, and mixtures thereof.

iii. Fatty Esters

Other suitable organic conditioning oils for use as the conditioningagent in the compositions of the present invention include, but are notlimited to, fatty esters having at least 10 carbon atoms. These fattyesters include esters with hydrocarbyl chains derived from fatty acidsor alcohols (e.g., mono-esters, polyhydric alcohol esters, and di- andtri-carboxylic acid esters). The hydrocarbyl radicals of the fattyesters hereof may include or have covalently bonded thereto othercompatible functionalities, such as amides and alkoxy moieties (e.g.,ethoxy or ether linkages, etc.).

Specific examples of preferred fatty esters include, but are not limitedto: iso-propyl isostearate, hexyl laurate, isohexyl laurate, isohexylpalmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecylstearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate,lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyloleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyladipate.

Other fatty esters suitable for use in the compositions of the presentinvention are mono-carboxylic acid esters of the general formula R′COOR,wherein R′ and R are alkyl or alkenyl radicals, and the sum of carbonatoms in R′ and R is at least 10, preferably at least 22.

Still other fatty esters suitable for use in the compositions of thepresent invention are di- and tri-alkyl and alkenyl esters of carboxylicacids, such as esters of C₄ to C⁸ dicarboxylic acids (e.g. C₁ to C₂₂esters, preferably C₁ to C₆, of succinic acid, glutaric acid, and adipicacid). Specific non-limiting examples of di- and tri-alkyl and alkenylesters of carboxylic acids include isocetyl stearyol stearate,diisopropyl adipate, and tristearyl citrate.

Other fatty esters suitable for use in the compositions of the presentinvention are those known as polyhydric alcohol esters. Such polyhydricalcohol esters include alkylene glycol esters, such as ethylene glycolmono and di-fatty acid esters, diethylene glycol mono- and di-fatty acidesters, polyethylene glycol mono- and di-fatty acid esters, propyleneglycol mono- and di-fatty acid esters, polypropylene glycol monooleate,polypropylene glycol 2000 monostearate, ethoxylated propylene glycolmonostearate, glyceryl mono- and di-fatty acid esters, polyglycerolpoly-fatty acid esters, ethoxylated glyceryl monostearate, 1,3-butyleneglycol monostearate, 1,3-butylene glycol distearate, polyoxyethylenepolyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylenesorbitan fatty acid esters.

Still other fatty esters suitable for use in the compositions of thepresent invention are glycerides, including, but not limited to, mono-,di-, and tri-glycerides, preferably di- and tri-glycerides, morepreferably triglycerides. For use in the compositions described herein,the glycerides are preferably the mono-, di-, and tri-esters of glyceroland long chain carboxylic acids, such as C₁₀ to C₂₂ carboxylic acids. Avariety of these types of materials can be obtained from vegetable andanimal fats and oils, such as castor oil, safflower oil, cottonseed oil,corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil,sesame oil, lanolin and soybean oil. Synthetic oils include, but are notlimited to, triolein and tristearin glyceryl dilaurate.

Other fatty esters suitable for use in the compositions of the presentinvention are water insoluble synthetic fatty esters. Some preferredsynthetic esters conform to the general Formula (VI):

wherein R¹ is a C₇ to C₉ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenylgroup, preferably a saturated alkyl group, more preferably a saturated,linear, alkyl group; n is a positive integer having a value from 2 to 4,preferably 3; and Y is an alkyl, alkenyl, hydroxy or carboxy substitutedalkyl or alkenyl, having from about 2 to about 20 carbon atoms,preferably from about 3 to about 14 carbon atoms. Other preferredsynthetic esters conform to the general Formula (VII):

wherein R² is a C₈ to C₁₀ alkyl, alkenyl, hydroxyalkyl or hydroxyalkenylgroup; preferably a saturated alkyl group, more preferably a saturated,linear, alkyl group; n and Y are as defined above in Formula (VII).

Specific non-limiting examples of suitable synthetic fatty esters foruse in the compositions of the present invention include: P-43 (C₈-C₁₀triester of trimethylolpropane), MCP-684 (tetraester of 3,3diethanol-1,5 pentadiol), MCP 121 (C₈-C₁₀ diester of adipic acid), allof which are available from Mobil Chemical Company.

c. Other Conditioning Agents

Also suitable for use in the compositions herein are the conditioningagents described in U.S. Pat. Nos. 5,674,478; 5,750,122; 4,529,586;4,507,280; 4,663,158; 4,197,865; 4,217, 914; 4,381,919; and 4,422, 853.

5. Anti-Dandruff Actives

The compositions of the present invention may also contain ananti-dandruff active. Suitable non-limiting examples of anti-dandruffactives include pyridinethione salts, azoles, selenium sulfide,particulate sulfur, keratolytic agents, and mixtures thereof. Suchanti-dandruff actives should be physically and chemically compatiblewith the essential components of the composition, and should nototherwise unduly impair product stability, aesthetics or performance.

Pyridinethione anti-microbial and anti-dandruff agents are described,for example, in U.S. Pat. No. 2,809,971; U.S. Pat. No. 3,236,733; U.S.Pat. No. 3,753,196; U.S. Pat. No. 3,761,418; U.S. Pat. No. 4,345,080;U.S. Pat. No. 4,323,683; U.S. Pat. No. 4,379,753; and U.S. Pat. No.4,470,982.

Azole anti-microbials include imidazoles such as climbazole andketoconazole.

Selenium sulfide compounds are described, for example, in U.S. Pat. No.2,694,668; U.S. Pat. No. 3,152,046; U.S. Pat. No. 4,089,945; and U.S.Pat. No. 4,885,107.

Sulfur may also be used as a particulate anti-microbial/anti-dandruffagent in the anti-microbial compositions of the present invention.

The present invention may further comprise one or more keratolyticagents such as salicylic acid.

Additional anti-microbial actives of the present invention may includeextracts of melaleuca (tea tree) and charcoal.

When present in the composition, the anti-dandruff active is included inan amount from about 0.01% to about 5%, preferably from about 0.1% toabout 3%, and more preferably from about 0.3% to about 2%, by weight ofthe composition.

6. Humectants

The compositions of the present invention may contain a humectant. Thehumectants herein are selected from the group consisting of polyhydricalcohols, water soluble alkoxylated nonionic polymers, and mixturesthereof. The humectants, when used herein, are preferably present in anamount by weight of the composition from about 0.1% to about 20%, morepreferably from about 0.5% to about 5%.

Polyhydric alcohols useful herein include glycerin, sorbitol, propyleneglycol, butylene glycol, hexylene glycol, ethoxylated glucose,1,2-hexane diol, hexanetriol, dipropylene glycol, erythritol, trehalose,diglycerin, xylitol, maltitol, maltose, glucose, fructose, sodiumchondroitin sulfate, sodium hyaluronate, sodium adenosine phosphate,sodium lactate, pyrrolidone carbonate, glucosamine, cyclodextrin, andmixtures thereof.

Water soluble alkoxylated nonionic polymers useful herein includepolyethylene glycols and polypropylene glycols having a molecular weightof up to about 1000 such as those with CTFA names PEG-200, PEG-400,PEG-600, PEG-1000, and mixtures thereof.

7. Suspending Agent

The compositions of the present invention may further comprise asuspending agent at concentrations effective for suspendingwater-insoluble material in dispersed form in the compositions or formodifying the viscosity of the composition. Such concentrations rangefrom about 0.1% to about 10%, preferably from about 0.3% to about 5.0%,by weight of the composition.

Suspending agents useful herein include anionic polymers and nonionicpolymers. Useful herein are vinyl polymers such as cross linked acrylicacid polymers with the CTFA name Carbomer, cellulose derivatives andmodified cellulose polymers such as methyl cellulose, ethyl cellulose,hydroxyethyl cellulose, hydroxypropyl methyl cellulose, nitro cellulose,sodium cellulose sulfate, sodium carboxymethyl cellulose, crystallinecellulose, cellulose powder, polyvinylpyrrolidone, polyvinyl alcohol,guar gum, hydroxypropyl guar gum, xanthan gum, arabia gum, tragacanth,galactan, carob gum, guar gum, karaya gum, carragheenin, pectin, agar,quince seed (Cydonia oblonga Mill), starch (rice, corn, potato, wheat),algae colloids (algae extract), microbiological polymers such asdextran, succinoglucan, pulleran, starch-based polymers such ascarboxymethyl starch, methylhydroxypropyl starch, alginic acid-basedpolymers such as sodium alginate, alginic acid propylene glycol esters,acrylate polymers such as sodium polyacrylate, polyethylacrylate,polyacrylamide, polyethyleneimine, and inorganic water soluble materialsuch as bentonite, aluminum magnesium silicate, laponite, hectonite, andanhydrous silicic acid.

Commercially available viscosity modifiers highly useful herein includeCarbomers with tradenames Carbopol 934, Carbopol 940, Carbopol 950,Carbopol 980, and Carbopol 981, all available from B.F. GoodrichCompany, acrylates/steareth-20 methacrylate copolymer with tradenameACRYSOL 22 available from Rohm and Hass, nonoxynyl hydroxyethylcellulosewith tradename AMERCELL POLYMER HM-1500 available from Amerchol,methylcellulose with tradename BENECEL, hydroxyethyl cellulose withtradename NATROSOL, hydroxypropyl cellulose with tradename KLUCEL, cetylhydroxyethyl cellulose with tradename POLYSURF 67, all supplied byHercules, ethylene oxide and/or propylene oxide based polymers withtradenames CARBOWAX PEGs, POLYOX WASRs, and UCON FLUIDS, all supplied byAmerchol.

Other optional suspending agents include crystalline suspending agentswhich can be categorized as acyl derivatives, long chain amine oxides,and mixtures thereof. These suspending agents are described in U.S. Pat.No. 4,741,855. These preferred suspending agents include ethylene glycolesters of fatty acids preferably having from about 16 to about 22 carbonatoms. More preferred are the ethylene glycol stearates, both mono anddistearate, but particularly the distearate containing less than about7% of the mono stearate. Other suitable suspending agents includealkanol amides of fatty acids, preferably having from about 16 to about22 carbon atoms, more preferably about 16 to 18 carbon atoms, preferredexamples of which include stearic monoethanolamide, stearicdiethanolamide, stearic monoisopropanolamide and stearicmonoethanolamide stearate. Other long chain acyl derivatives includelong chain esters of long chain fatty acids (e.g., stearyl stearate,cetyl palmitate, etc.); long chain esters of long chain alkanol amides(e.g., stearamide diethanolamide distearate, stearamide monoethanolamidestearate); and glyceryl esters (e.g., glyceryl distearate,trihydroxystearin, tribehenin) a commercial example of which is Thixin Ravailable from Rheox, Inc. Long chain acyl derivatives, ethylene glycolesters of long chain carboxylic acids, long chain amine oxides, andalkanol amides of long chain carboxylic acids in addition to thepreferred materials listed above may be used as suspending agents.

Other long chain acyl derivatives suitable for use as suspending agentsinclude N,N-dihydrocarbyl amido benzoic acid and soluble salts thereof(e.g., Na, K), particularly N,N-di(hydrogenated) C.sub.16, C.sub.18 andtallow amido benzoic acid species of this family, which are commerciallyavailable from Stepan Company (Northfield, Ill., USA).

Examples of suitable long chain amine oxides for use as suspendingagents include alkyl dimethyl amine oxides, e.g., stearyl dimethyl amineoxide.

Other suitable suspending agents include primary amines having a fattyalkyl moiety having at least about 16 carbon atoms, examples of whichinclude palmitamine or stearamine, and secondary amines having two fattyalkyl moieties each having at least about 12 carbon atoms, examples ofwhich include dipalmitoylamine or di(hydrogenated tallow)amine. Stillother suitable suspending agents include di(hydrogenated tallow)phthalicacid amide, and crosslinked maleic anhydride-methyl vinyl ethercopolymer.

8. Other Optional Components

The compositions of the present invention may contain other optionalcomponents. Optional components may be present in the dispersed gelnetwork phase or may be added to the final shampoo composition asseparate components.

For example, the compositions of the present invention may containwater-soluble and water-insoluble vitamins such as vitamins B1, B2, B6,B12, C, pantothenic acid, pantothenyl ethyl ether, panthenol, biotin andtheir derivatives, and vitamins A, D, E, and their derivatives. Thecompositions of the present invention may also contain water-soluble andwater-insoluble amino acids such as asparagine, alanine, indole,glutamic acid and their salts, and tyrosine, tryptamine, lysine,histadine and their salts. The compositions of present invention mayfurther comprise materials useful for hair loss prevention and hairgrowth stimulants or agents.

The compositions of the present invention also may comprise materialsselected from the group consisting of sugar amines (e.g.,N-acetylglucosamine), vitamin B3 compounds, sodium dehydroacetate,dehydroacetic acid and its salts, phytosterols, soy derivatives (e.g.,equol and other isoflavones), niacinamide, phytantriol, farnesol,bisabolol, salicylic acid compounds, hexamidines, dialkanoylhydroxyproline compounds, flavonoids, N-acyl amino acid compounds,retinoids (e.g., retinyl propionate), water-soluble vitamins, ascorbates(e.g., vitamin C, ascorbic acid, ascorbyl glucoside, ascorbyl palmitate,magnesium ascorbyl phosphate, sodium ascorbyl phosphate), sunscreenactives, anti-cellulite agents, butylated hydroxytoluene, butylatedhydroxyanisole, their derivatives, and combinations thereof.

Any other suitable optional component can also be included in thecomposition of the present invention, such as those ingredients that areconventionally used in given product types. The CTFA Cosmetic IngredientHandbook, Tenth Edition (2004), published by the Cosmetic, Toiletry, andFragrance Association, Inc., Washington, D.C., describes a wide varietyof nonlimiting materials that can be added to the composition herein.Examples of these ingredient classes include, but are not limited to:abrasives, absorbents, aesthetic components such as perfumes andfragrances, pigments, colorings/colorants, essential oils, skinsensates, astringents, etc. (e.g., clove oil, menthol, camphor,eucalyptus oil, eugenol, menthyl lactate, witch hazel distillate),anti-acne agents, anti-caking agents, antifoaming agents, antimicrobialagents (e.g., iodopropyl butylcarbamate), antibacterial agents,antifungal agents, antioxidants, binders, biological additives,buffering agents, bulking agents, chelating agents, chemical additives,colorants, cosmetic astringents, cosmetic biocides, denaturants, drugastringents, external analgesics, film formers or materials, e.g.,polymers, for aiding the film-forming properties and substantivity ofthe composition (e.g., copolymer of eicosene and vinyl pyrrolidone),opacifying agents, pH adjusters, plant derivatives, plant extracts,plant tissue extracts, plant seed extracts, plant oils, botanicals,botanical extracts, preservatives, propellants, reducing agents, sebumcontrol agents, sequestrants, skin bleaching and lightening agents,(e.g., hydroquinone, kojic acid, ascorbic acid, magnesiuim ascorbylphosphate, ascorbyl glucoside, pyridoxine), enzymes, coenzymes,skin-conditioning agents (e.g., humectants and occlusive agents), skinsoothing and/or healing agents and derivatives (e.g., panthenol, andderivatives such as ethyl panthenol, aloe vera, pantothenic acid and itsderivatives, allantoin, bisabolol, and dipotassium glycyrrhizinate),skin treating agents (e.g., vitamin D compounds, mono-, di-, andtri-terpenoids, beta-ionol, cedrol), thickeners (including a mono- ordivalent salt such as sodium chloride), and vitamins, their derivatives,and combinations thereof.

E. Process of Making a Shampoo Composition

An aspect of the invention relates to a process of making a shampoocomposition of the present invention. The process of making a shampoocomposition comprises (a) combining a fatty amphiphile, a secondarysurfactant, and water at a temperature sufficient to allow partitioningof the secondary surfactant and the water into the fatty amphiphile toform a pre-mix; (b) cooling the pre-mix below the chain melt temperatureof the fatty amphiphile to form a gel network; (c) adding the gelnetwork to one or more detersive surfactants and an aqueous carrier toform a shampoo composition.

As discussed above, in one embodiment of the present invention, the gelnetwork component is prepared as a separate pre-mix, which, after beingcooled, is subsequently incorporated with the other components of theshampoo composition. More specifically, the gel network component of thepresent invention may be prepared by heating the fatty amphiphile, thesecondary surfactant, and water to a level in the range of about 75° C.to about 90° C. and mixing. This mixture is cooled to a level in therange of about 27° C. to about 35° C. by, for example, passing themixture through a heat exchanger. As a result of this cooling step, thefatty amphiphile and the secondary surfactant crystallize to form acrystalline gel network.

Alternative methods of preparing the gel network component includesonication and/or milling of the fatty amphiphile, the secondarysurfactant, and water, while these components are heated, to reduce theparticle size of the melted fatty amphiphile phase. This results in anincrease in surface area of the fatty amphiphile phase, which allows thesecondary surfactant and the water to swell the fatty amphiphile phase.Another suitable variation in preparing the gel network includes heatingand mixing the fatty amphiphile and the secondary surfactant first, andthen adding that mixture to the water.

F. Method of Use

The compositions of the present invention are used in a conventionalmanner for cleansing and conditioning hair or skin, including scalp,face, and body. Generally, a method of treating hair or skin of thepresent invention comprises applying the composition of the presentinvention to the hair or skin. More specifically, an effective amount ofthe personal care composition is applied to the hair or skin, which haspreferably been wetted with water, and then the personal carecomposition is rinsed off. Such effective amounts generally range fromabout 1 g to about 50 g, preferably from about 1 g to about 20 g.Application to the hair typically includes working the compositionthrough the hair such that most or all of the hair is contacted with thecomposition.

The method for treating the hair or skin comprises the steps of: (a)wetting the hair or skin with water; (b) applying an effective amount ofthe shampoo composition to the hair or skin, and (c) rinsing the appliedareas of skin or hair with water. These steps can be repeated as manytimes as desired to achieve the desired cleansing and conditioningbenefit.

In one embodiment, the shampoo composition of the present inventionadvantageously is used to treat damaged hair. Damaged hair may includehair selected from permed hair, oxidatively colored hair, andmechanically damaged hair.

In another embodiment, the shampoo composition is used to treat skin,such as the scalp, the face, and the body.

The personal care compositions of this invention may be used as liquids,solids, semi-solids, flakes, gels, placed in a pressurized containerwith a propellant added, or used in a pump spray form. The viscosity ofthe product may be selected to accommodate the form desired.

NON-LIMITING EXAMPLES

The shampoo compositions illustrated in the following Examplesillustrate specific embodiments of the shampoo compositions of thepresent invention, but are not intended to be limiting thereof. Othermodifications can be undertaken by the skilled artisan without departingfrom the spirit and scope of this invention. These exemplifiedembodiments of the shampoo composition of the present invention provideenhanced conditioning benefits to the hair.

The shampoo compositions illustrated in the following Examples areprepared by conventional formulation and mixing methods, an example ofwhich is set forth hereinbelow. All exemplified amounts are listed asweight percents and exclude minor materials such as diluents,preservatives, color solutions, imagery ingredients, botanicals, and soforth, unless otherwise specified. All percentages are based on weightunless otherwise specified.

Preparation of the Gel Network Pre-Mix

To prepare the gel network pre-mix, about 20% of the water is heated toabout 74° C. and the fatty amphiphile and the secondary surfactant(e.g., Behenyltrimethylammonium chloride (Varisoft BT-85) or SodiumLaureth Sulfate) are added to it. After incorporation, this mixture ispassed through a mill and heat exchanger where it is cooled to about 35°C. As a result of this cooling step, the fatty amphiphile, the secondarysurfactant, and the water form a crystalline gel network.

For mixtures of different fatty amphiphiles, it may be beneficial topre-mix the fatty amphiphile materials before incorporation into thewater. This can be done by co-melting the different fatty amphiphilestogether and utilizing this melt or cooling into a solid phase andincorporating this into the heated water along with the secondarysurfactant. Another variation could be to co-melt the one or more fattyamphiphiles and the secondary surfactant before incorporation into thewater. Some gel network compositions with chain melt temperaturesbetween about 27° C. to about 35° C. will need to be cooled below 27° C.to ensure the lamellar phase structure is froze.

Gel Network Pre-Mix Examples 1-70

The following Examples illustrate specific embodiments of the gelnetwork pre-mix, prior to its incorporation with the detersivesurfactant and other components of the final shampoo composition of thepresent invention. It is intended that each of the following gel networkpre-mix examples could be incorporated as a dispersed phase into ashampoo composition according to the present invention.

Ingredient 1 2 3 4 5 6 7 Water 88.55% 88.55% 88.55% 88.55% 88.55% 88.55%88.55% Behenamidopropyl 8.58% dimethylamine, Incromine BB (2) Glyceryldistearate (1) 8.58% Glyceryl hydroxystearate (1) 8.58% Glycerylpalmitate (1) 8.58% Glyceryl stearate, Glyceryl 8.58% Stearate Pure (1)Oleamide, Croadmide VRX Bead (2) 8.58% Palmitic acid (3) 8.58%Behenyltrimethylammonium 2.84% 2.84% 2.84% 2.84% 2.84% 2.84% 2.84%chloride, Varisoft BT-85 (4) 5-Chloro-2-methyl-4-isothiazolin- 0.03%0.03% 0.03% 0.03% 0.03% 0.03% 0.03% 3-one, Kathon CG Ingredient 8 9 1011 12 13 14 Water 88.55% 88.55% 88.55% 88.55% 88.55% 88.55% 88.55% PEG-2Stearate (1) 8.58% PEG-5 Glyceryl stearate (1) 8.58% PEG-6 Stearate (1)8.58% SEFA Stearate, Sefose-1618H (3) 8.58% Sorbitan palmitate (1) 8.58%Sorbitan stearate, Grill 3 NF (2) 8.58% Sorbitan stearate(1) 8.58%Behenyltrimethylammonium 2.84% 2.84% 2.84% 2.84% 2.84% 2.84% 2.84%chloride, Varisoft BT-85 (4) 5-Chloro-2-methyl-4-isothiazolin- 0.03%0.03% 0.03% 0.03% 0.03% 0.03% 0.03% 3-one, Kathon CG Ingredient 15 16 1718 19 20 21 Water 88.55% 88.55% 88.55% 88.55% 88.55% 88.55% 88.55%Glyceryl palmitate (1) 4.29% Glyceryl stearate, Glyceryl 4.29% StearatePure (1) Sorbitan tristearate (1) 8.58% Stearamide MEA-stearate (1)8.58% Steareth-2, Volpo S-2 (2) 8.58% 6.44% Stearic acid, V-1890 (3)8.58% 2.14% Sucrose distearate, Crodesta F-10 (2) 8.58%Behenyltrimethylammonium 2.84% 2.84% 2.84% 2.84% 2.84% 2.84% 2.84%chloride, Varisoft BT-85 (4) 5-Chloro-2-methyl-4-isothiazolin- 0.03%0.03% 0.03% 0.03% 0.03% 0.03% 0.03% 3-one, Kathon CG Ingredient 22 23 2425 26 27 28 Water 82.75% 82.75% 82.75% 82.75% 82.75% 82.75% 82.75%Behenamidopropyl 8.58% dimethylamine, Incromine BB (2) Glyceryldistearate (1) 8.58% Glyceryl hydroxystearate (1) 8.58% Glycerylpalmitate (1) 8.58% Glyceryl stearate, Glyceryl 8.58% Stearate Pure (1)Oleamide, Crodamide VRX Bead (2) 8.58% Palmitic acid, V-1695 (3) 8.58%Sodium laureth-3 sulfate (28% 8.64% 8.64% 8.64% 8.64% 8.64% 8.64% 8.64%Active) 5-Chloro-2-methyl-4-isothiazolin- 0.03% 0.03% 0.03% 0.03% 0.03%0.03% 0.03% 3-one, Kathon CG Ingredient 29 30 31 32 33 34 35 Water82.75% 82.75% 82.75% 82.75% 82.75% 82.75% 82.75% PEG-2 Stearate (1)8.58% PEG-5 Glyceryl stearate (1) 8.58% PEG-6 Stearate (1) 8.58% SEFAStearate, Sefose-1618H (3) 8.58% Sorbitan palmitate (1) 8.58% Sorbitanstearate, Crill 3 NF (2) 8.58% Sorbitan stearate (1) 8.58% Sodiumlaureth-3 sulfate (28% 8.64% 8.64% 8.64% 8.64% 8.64% 8.64% 8.64% Active)5-Chloro-2-methyl-4-isothiazolin- 0.03% 0.03% 0.03% 0.03% 0.03% 0.03%0.03% 3-one, Kathon CG Ingredient 36 37 38 39 40 41 42 Water 82.75%82.75% 82.75% 86.14% 82.75% 82.75% 82.75% Cetyl Alcohol 3.46% Cocamineoxide 4.30% Glyceryl distearate (1) 4.30% Sorbitan tristearate (1) 8.58%Steary Alcohol 6.44% Stearamide MEA-stearate (1) 8.58% Steareth-2, VolpaS-2 (2) 8.58% Stearic acid, V-1890 (3) 4.28% Sucrose distearate,Crodesta F-10 (2) 8.58% 4.28% Sodium laureth-3 sulfate (28% 8.64% 8.64%8.64% 3.93% 8.64% 8.64% 8.64% Active) 5-Chloro-2-methyl-4-isothiazolin-0.03% 0.03% 0.03% 0.03% 0.03% 0.03% 0.03% 3-one, Kathon CG Ingredient 4344 45 46 47 48 49 Water 88.78% 88.78% 88.78% 88.78% 88.78% 88.78% 88.78%Behenamidopropyl 9.90% dimethylamine, Incromine BB (2) Glyceryldistearate (1) 9.90% Glyceryl hydroxystearate (1) 9.90% Glycerylstearate, Glyceryl 9.90% Stearate Pure (1) PEG-2 Stearate (1) 9.90%PEG-6 Stearate (1) 9.90% Sorbitan stearate, Crill 3 NF (2) 9.90%Behenyltrimethylammonium 1.29% 1.29% 1.29% 1.29% 1.29% 1.29% 1.29%chloride, Varisoft BT-85 (2) 5-Chloro-2-methyl-4-isothiazolin- 0.03%0.03% 0.03% 0.03% 0.03% 0.03% 0.03% 3-one, Kathon CG Ingredient 50 51 5253 54 55 56 Water 88.78% 88.55% 88.78% 88.78% 88.78% 88.78% 88.78%Glyceryl distearate (1) 4.95% Stearyl Alcohol 5.57% 2.48% 3.21% CetylAlcohol 3.00% 2.47% 1.74% Glyceryl hydroxystearate (1) 4.95% PEG-2Stearate (1) 4.95% Stearamide MEA-stearate (1) 9.90% Steareth-2, VolpoS-2 (2) 4.95% 4.95% Stearic acid, V-1890 (3) 4.95% 4.95% 4.95% 4.95%4.95% Behenyltrimethylammonium 1.29% 2.85% 1.29% 1.29% 1.29% 1.29% 1.29%chloride, Varisoft BT-85 (2) 5-Chloro-2-methyl-4-isothiazolin- 0.03%0.03% 0.03% 0.03% 0.03% 0.03% 0.03% 3-one, Kathon CG Ingredient 57 58 5960 61 62 63 Water 86.14% 86.14% 86.14% 86.14% 86.14% 86.14% 86.14%Glyceryl distearate (1) 9.90% 4.950% Glyceryl stearate, Glyceryl 9.90%4.950% Stearate Pure (1) PEG-2 Stearate (1) 9.90% 4.950% Steareth-2,Volpo S-2 (2)  9.90%  4.95% Stearic acid, V-1890 93)  4.95%  4.95%Sodium laureth-3 sulfate (28% 3.93% 3.93% 3.93% 3.93% 3.93%  3.93% 3.93% Active) 5-Chloro-2-methyl-4-isothiazolin- 0.03% 0.03% 0.03% 0.03%0.03%  0.03%  0.03% 3-one, Kathon CG Ingredient 64 65 66 67 68 69 70Water 87.13% 82.13% 77.13% 72.13% 67.13% 77.13% 77.13% Cetyl Alcohol3.50% 5.25% 7.00% 8.75% 10.50% 7.00% 7.00% Glyceryl palmitate (1) 6.50%Oleyl Alcohol 1.00% Sorbitan stearate (1) 6.50% Stearyl Alcohol 6.50%9.75% 13.00% 16.25% 19.50% 5.50% 6.50% Behenyltrimethylammonium 2.84%2.84% 2.84% 2.84% 2.84% 2.84% 2.84% chloride, Varisoft BT-85 (4)5-Chloro-2-methyl-4-isothiazolin- 0.03% 0.03% 0.03% 0.03% 0.03% 0.03%0.03% 3-one, Kathon CG (1) available from A&E Connock (2) available fromCroda Chemicals (3) available from P&G Chemicals (4) availableGoldschmidt Chemical

Preparation of Final Shampoo Compositions

To prepare the final shampoo composition, first, a surfactant solutionpre-mix is formed. To prepare this surfactant solution pre-mix, about 6%to about 9% of sodium or ammonium laureth-3 sulfate, cationic polymers,and about 0% to about 5% of water are added to a jacketed mix tank andheated to about 74° C. with agitation. To this solution, citric acid,sodium citrate, sodium benzoate, and disodium EDTA are added to the tankand allowed to disperse. Ethylene glycol distearate (EGDS) is then addedto the mixing vessel and melted. After the EGDS was well dispersed(e.g., after about 10 minutes), preservative is added and mixed into thesurfactant solution. This mixture is passed through a mill and heatexchanger where it is cooled to about 35° C. and collected in afinishing tank. As a result of this cooling step, the EGDS crystallizesto form a waxy crystalline suspension. The mixture of these componentsis the surfactant solution pre-mix.

Next, the surfactant solution pre-mix and the gel network pre-mix, whichis prepared as described above, are mixed together. The remainder of thesurfactants, perfume, dimethicone, sodium chloride or ammonium xylenesulfonate for viscosity adjustment, and the remainder of the water areadded with ample agitation to ensure a homogeneous mixture. This mixtureis the final shampoo composition which comprises as a dispersed phasethe gel network pre-mix.

Preferred viscosities of the final shampoo composition according to thepresent invention range from about 5000 to about 15,000 centipoise at27° C., as measured by a Wells-Brookfield model RVTDCP viscometer usinga CP-41 cone and plate at 2/s at 3 minutes.

The pH may be adjusted as necessary to provide shampoo compositions ofthe present invention which are suitable for application to human hair,and may vary based on the selection of particular detersive surfactants,fatty amphiphiles, and/or other components.

Shampoo Examples 1-20

The following Examples illustrate specific embodiments of the finalshampoo composition of the present invention, which respectivelycomprise select above-exemplified gel network pre-mixes as a dispersedphase.

Ingredient 1 2 3 4 5 6 7 8 9 10 Sodium Laureth 10.00 10.00 10.00 10.0010.00 10.00 10.00 10.00 10.00 7.65 Sulfate Sodium Lauryl 1.50 1.50 1.501.50 1.50 6.00 6.00 6.00 6.00 6.35 Sulfate Cocamidopropyl 2.00 2.00 2.003.00 3.00 betaine Cocamide MEA 0.60 Any one of Gel 27.27 27.27 27.2727.27 27.27 13.64 6.82 27.27 Networks 1-21 Gel Network 39 27.27 GelNetwork 51 27.27 Guar 0.40 Hydroxypropyl trimonium chloride (1) Guar0.40 Hydroxypropyl trimonium chloride (2) Guar 0.40 0.20 0.40Hydroxypropyl trimonium chloride (3) Guar 0.20 Hydroxypropyl trimoniumchloride (4) Polyquaterium-10 (5) 0.40 Polyquaterium-10 (6) 0.40Polyquaterium-10 (7) 0.40 0.40 PEG-7M (8) 0.10 Dimethicone (9) 2.00 2.002.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Ethylene Glycol 1.50 1.50 1.501.50 1.50 1.50 1.50 1.50 1.50 1.50 Distearate 5-Chloro-2- 0.0005 0.00050.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 methyl-4-isothiazolin-3-one, Kathon CG Sodium Benzoate 0.25 0.25 0.25 0.25 0.250.25 0.25 0.25 0.25 0.25 Disodium EDTA 0.13 0.13 0.13 0.13 0.13 0.130.13 0.13 0.13 0.13 Perfume 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.700.70 Citric Acid/ pH pH pH pH pH pH pH pH pH pH Sodium Citrate QS QS QSQS QS QS QS QS QS QS Dihydrate Sodium Chloride/ Visc. Visc. Visc. Visc.Visc. Visc. Visc. Visc. Visc. Visc. Ammonium QS QS QS QS QS QS QS QS QSQS Xylene Sulfonate Water QS QS QS QS QS QS QS QS QS QS Ingredient 11 1213 14 15 16 17 18 19 20 Sodium Laureth 10.00 7.65 7.65 7.65 7.65 SulfateSodium Lauryl 1.50 6.35 6.35 6.35 6.35 Sulfate Ammonium 10.00 6.00 12.0012.00 10.00 Laureth Sulfate Ammonium Lauryl 6.00 10.00 2.00 2.00 2.00Sulfate Sodium 2.00 2.00 2.00 Lauroamphoacetate Cocamidopropyl 2.00 2.00betaine Cocamide MEA 0.60 Any one of Gel 27.27 27.27 27.27 27.27 27.2727.27 Networks 1-21 Gel Networks 64-68 27.27 13.64 6.82 27.27 Guar 0.400.40 0.40 Hydroxypropyl trimonium chloride (3) Polyquaterium-10 (6) 0.10PEG-7M (8) Dimethicone (9) 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00Dimethicone (10) 2.00 2.00 Ethylene Glycol 1.50 1.50 1.50 1.50 1.50 1.501.50 1.50 1.50 1.50 Distearate 5-Chloro-2- 0.0005 0.0005 0.0005 0.00050.0005 0.0005 0.0005 0.0005 0.0005 0.0005 methyl-4- isothiazolin-3-one,Kathon CG Sodium Benzoate 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.250.25 Disodium EDTA 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13Perfume 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.70 0.70 Citric Acid/pH pH pH pH pH pH pH pH pH pH Sodium Citrate QS QS QS QS QS QS QS QS QSQS Dihydrate Sodium Chloride/ Visc. Visc. Visc. Visc. Visc. Visc. Visc.Visc. Visc. Visc. Ammonium QS QS QS QS QS QS QS QS QS QS XyleneSulfonate Water QS QS QS QS QS QS QS QS QS QS (1) Jaguar C17 availablefrom Rhodia (2) N-Hance 3269 (with Mol. W. of ~500,000 and 0.8 meq/g)available from Aqulaon/Hercules (3) ADPP-5043HMW (with Mol. W. of~1,200,000 and Char.Den. of 2.0 meq/g) available from Aqualon/Hercules(4) ADPP-5043 LMW (with Mol. W. of ~500,000 and Char.Den. of 2.0 meq/g)available from Aqulaon/Hercules (5) Polymer JR30M available fromAmerchol/Dow Chemical (6) Polymer LR30M available from Amerchol/DowChemical (7) Polymer KG30M available from Amerchol/Dow Chemical (8)Peg-7M Available from Amerchol/Dow Chemical (9) Viscasil 330M availablefrom General Electric Silicones (10) DC1664 available from Dow CorningSilicones

The fatty amphiphile deposition of these products is measured bytreating a switch of hair with 3 cycles (2 lather/rinse steps per cycle,0.1 g shampoo per g hair on each lather/rinse step) with the shampoo.Four switches are treated with each shampoo. The switches are thenextracted with solvent and the level of adsorbed fatty amphiphilemeasured by gas chromatographic-mass spectrophotometric analysis of theextracts.

Analytical Methods and Examples

The following provides example X-ray analysis data and exampledifferential scanning calorimetry (“DSC”) data for several of theabove-exemplified compositions.

X-Ray Data X-Ray Data DSC Melt (WAXD) (SAXS) Transition Fatty ChainLamellar Temperature d-spacing** d-spacing** for Gel Network* GelNetwork 4.13 Å 247 Å 67° C. Example # 39 Gel Network 4.13 Å 270 Å 74° C.Example # 51 Shampoo 4.13 Å 93 Å 38° C. Example # 5 Shampoo 4.13 Å 93 Å38° C. Example # 4 *See Differential Scanning Calorimetry method forsample preparation and analysis techniques. **See X-Ray method forsample preparation and analysis techniques.Differential Scanning Calorimetry Method

The chain melt temperature of the layer in the gel network comprisingthe one or more fatty amphiphiles (i.e., the melt transition temperaturefor the gel network) may be obtained using differential scanningcalorimetry according to the following method. Utilizing a TAInstruments Q100 DSC, approximately 50 mg of the gel network pre-mix orthe final shampoo composition containing the gel network is placed intoa stainless steel high volume DSC pan. The sample, along with an emptyreference pan is placed into the instrument. The samples are analyzedusing the following conditions/temperature program: Nitrogen Purge,Equilibrate @5.00° C. until an isothermal is reach for 2.00 min. Rampthe temperature at a rate of 3.00° C./min to 90.00° C. Each sample isanalyzed in duplicate. The resulting DSC data is analyzed using TAInstruments Universal Analysis Software.

The use of DSC to measure the melt transition temperature for gelnetworks is further described by T. de Vringer et al., Colloid andPolymer Science, vol. 265, 448-457 (1987); and H. M. Ribeiro et al.,Intl. J. of Cosmetic Science, vol. 26, 47-59 (2004).

X-Ray Analysis Method

Small-angle x-ray scattering (“SAXS”) as used to resolve periodicstructures in mesophases is essentially an x-ray diffraction technique.It is used in conjunction with conventional wide-angle x-ray diffraction(“WXRD”) to characterize aggregate structures such as micelles, gelnetworks, lamella, hexagonal and cubic liquid crystals. The differentmesophases that show periodic structures can be characterized by therelative positions (d-spacing) of their reflections as derived from theBragg equation (d=λ/2 Sin θ) where d represents the interplanar spacing,λ the radiation wavelength and θ the scattering (diffraction) angle.

The one dimensional lamella gel network phase is characterized by theratio of the interplanar spacings d₁/d₁, d₁/d₂, d₁/d₃, d₁/d₄, d₁/d₅having the values 1:2:3:4:5 etc. in the SAXS region (long-range order)and one or two invariant reflection(s) in the WXRD region (short-range)centered around 3.5 and 4.5 Å over a broad halo background. Othermesophases (e.g. hexagonal or cubic) will have characteristicallydifferent d-spacing ratios.

WXRD data are collected in transmission mode on a Stoe STADI-Pdiffractometer equipped with an image plate position-sensitive detector.The specimen is positioned between two milar films in the sample holderand placed in the path of the x-ray beam. The IP detector has a solidangle of about 120° 2θ and records diffracted x-ray beamssimultaneously. Data are collected and analyzed using the XPOW software.

SAXS data are collected on Rigaku rotating anode generator with a finefocus filament equipped with a HI-STAR 2-dimensional area detector fromBruker-AXS. The setup has an evacuated chamber, which houses thespecimen, conjoined with an evacuated tube leading to the detector toreduce air scatter. The specimen sample holder consists of copper plateswith small rectangular cavities to hold the fluid-like material and alsoallow the transmission of the x-ray beam. The openings to the cavitiesare sealed with kapton windows to provide leak-free environment undervacuum. The 2-D data are azimuthally integrated and reduced to intensityversus scattering vector (q) or its d equivalent by a combination ofGADDS software and in-house software modules implementing knowntechniques on the Igor platform.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A shampoo composition comprising: a) from about 5% to about 50% ofone or more anionic detersive surfactants, by weight of said shampoocomposition; b) from about 5% to about 40% by weight of said shampoocomposition of a preformed solid crystalline gel network phaseconsisting of: i) from about 0.05% to about 14% by weight of saidshampoo composition of one or more fatty amides, fatty alkanolamides,and fatty alkoxylated amides selected from the group consisting ofCocamide, Cocamide Methyl MEA, Cocoyl Glutamic Acid, Erucamide,Lauramide, Oleamide, Palmitamide, Stearamide, Stearyl Erucamide,Behenamide DEA, Behenamide MEA, Cocamide DEA, Cocamide MEA, CocamideMIPA, Hydroxyethyl Stearamide-MIPA, Hydroxypropyl Bisisostearamide MEA,Hydroxypropyl Bislauramide MEA, Hydroxystearamide MEA, IsostearamideDEA, Isostearamide MEA, Isostearamide MIPA, Lauramide DEA, LauramideMEA, Lauramide MIPA, Myristamide DEA, Myristamide MEA, Myristamide MIPA,Palmamide DEA, Palmamide MEA, Palmamide MIPA, Palmitamide DEA,Palmitamide MEA, PEG-20 Cocamide MEA, Stearamide AMP, Stearamide DEA,Stearamide DEA-Distearate, Stearamide DIBA-Stearate, Stearamide MEA,Stearamide MEA-Stearate, Stearamide MIPA, PEG-2 Cocamide, PEG-3Cocamide, PEG-4 Cocamide, PEG-5 Cocamide, PEG-6 Cocamide, PEG-7Cocamide, PEG-3 Lauramide, PEG-5 Lauramide, PEG-3 Oleamide, PEG-9Oleamide, PEG-4 Stearamide, PEG-10 Stearamide, PPG-2 Cocamide, PPG-2Hydroxyethyl Cocamide, PPG-2 Hydroxyethyl Coco/Isostearamide, Ceramide1, Ceramide 2, Ceramide 3, Ceramide 4, Ceramide 5, and mixtures thereof;ii) from about 0.3 to about 5% by weight of said shampoo composition ofone or more cationic surfactants selected from the group consisting ofcetrimonium chloride, stearimonium chloride, behentrimonium chloride,behentrimonium methosulfate, behenamidopropyltrimonium methosulfate,stearamidopropyltrimonium chloride, arachidtrimonium chloride,distearyldimonium chloride, iii) water; wherein said one or more fattyamides, fatty alkanolamides, and fatty alkoxylated amides selected fromgroup (i) are present relative to said cationic surfactant at a weightratio of from about 2:1 to about 10:1, c) from about 20% to about 95% ofan aqueous carrier, by weight of said shampoo composition.
 2. A shampoocomposition according to claim 1, further comprising a deposition aid.3. A shampoo composition according to claim 2, wherein said depositionaid is a cationic polymer.
 4. A shampoo composition according to claim3, wherein said cationic polymer has a molecular weight from about10,000 to about 10,000,000 and a charge density from about 0.9 meq/g toabout 7.0 meq/g.
 5. A shampoo composition according to claim 4, whereinsaid charge density is from about 1.0 meq/g to about 3.5 meq/g.
 6. Ashampoo composition according to claim 1, further comprising asuspending agent.
 7. A shampoo composition according to claim 6, whereinsaid suspending agent is a crystalline suspending agent.
 8. A processfor preparing a shampoo composition according to claim 1, said processcomprising the steps of: a) combining one or more fatty amides, fattyalkanolamides, and fatty alkoxylated amides selected from group (i), acationic surfactant, and water at a temperature sufficient to allowpartitioning of said cationic surfactant, and said water into said oneor more fatty amides, fatty alkanolamides, and fatty alkoxylated amidesselected from group (i), to form a pre-mix; b) cooling said pre-mixbelow the chain melt temperature of said one or more fatty amides, fattyalkanolamides, and fatty alkoxylated amides selected from group (i), toform a preformed solid crystalline gel network phase; c) adding saidpreformed solid crystalline gel network phase to one or more anionicdetersive surfactants and an aqueous carrier to form a shampoocomposition.